N-pyridinium and n-ARYL aziridines as aspartate and glutamate selective covalent ligands and uses thereof

Abstract

This invention is in the field of chemistry and contemplates pyridinium aziridine and aryl aziridine compounds, methods for synthesis, target identification, and biological evaluation of a novel class of chemical compounds for covalent targeting of aspartate and glutamate residues on disease-relevant proteins to expand the scope of the currently accessible druggable proteome and pharmaceutical compositions, such as protein inhibitors, and methods of use thereof.

Description

[0001] N-PYRIDINIUM AND N-ARYL AZIRIDINES AS ASPARTATE AND GLUTAMATE SELECTIVE COVALENT LIGANDS AND USES THEREOF CROSS REFERENCE TO RELATED APPLICATIONS The present application claims the benefit of U.S. Provisional Patent Applications 63 / 712,975, filed October 28, 2024 and 63 / 634,690, filed April 16, 2024, which is incorporated herein by reference. STATEMENT OF GOVERNMENTAL SUPPORT This invention was made with government support under grant number R35GM138114 awarded by the National Institutes of Health. The government has certain rights in the invention. FIELD OF THE INVENTION This invention is in the field of chemistry and describes pyridinium aziridine and aryl aziridine compounds, methods for synthesis, target identification, and biological evaluation of a novel class of chemical compounds for covalent targeting of aspartate and glutamate residues on disease-relevant proteins to expand the scope of the currently accessible druggable proteome and pharmaceutical compositions, such as protein inhibitors, and methods of use thereof. The compounds described herein can be used for disease treatment and as research tools. BACKGROUND OF THE INVENTION The current challenge in drug discovery revolves around the limited availability of proteins that can be effectively targeted by small molecule drugs. As a resurging strategy to expand the druggable targets, covalent targeting, unlike traditional methods, forms enduring bonds between drugs and specific amino acids on the targets, allowing for engagement with proteins lacking accessible binding sites or complex structures. The invention focuses on developing N-pyridinium aziridines and N-aryl aziridines as covalent inhibitors to selectively target residues, particularly aspartic and glutamic acid residues, broadening the range of targetable amino acid residues beyond those typically addressed by existing covalent chemistry strategies. These molecules, featuring an aziridine core component, offer new opportunities for discovering novel covalent drug candidates by exploring their proteomic target landscape. SUMMARY OF THE INVENTION This invention is described in preferred embodiments in the following description with reference to the Figures, in which like numbers represent the same or similar elements. Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment. The described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are recited to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention. This invention is in the field of chemistry and describes pyridinium aziridine and aryl aziridine compounds, methods for synthesis, target identification, and biological evaluation of a novel class of chemical compounds for covalent targeting of aspartate and glutamate residues on disease-relevant proteins to expand the scope of the currently accessible druggable proteome and pharmaceutical compositions, such as protein inhibitors, and methods of use thereof. The compounds described herein can be used for disease treatment and as research tools. In one embodiment, the invention relates to a method of olefin activation that is not visible- light-induced. It is not photocatalyzed. As a result, it can be done in the dark, i.e. in the absence of light or without the need for light. Thus, in one embodiment, the invention relates to a method of olefin activation comprising; a) providing; i) an N-aminopyridinium salt; ii) at least one unactivated alkene; and iii) a hypervalent iodine reagent; and b) reacting said unactivated alkene with said N-aminopyridinium in the presence of said hypervalent iodine reagent so as create a pyridinium aziridine compound, wherein the reaction takes place without the need for light. In one embodiment, said method is metal free. In one embodiment, said method is catalyst free. In one embodiment, the invention relates to a method of catalyst-free olefin activation in the dark comprising; a) providing; i) an N-aminopyridinium salt; ii) at least one unactivated alkene; and iii) a hypervalent iodine reagent; and b) reacting said unactivated alkene with said N-aminopyridinium in the presence of said hypervalent iodine reagent so as create a pyridinium aziridine compound. In addition to the method, the present invention also contemplates these resultant compounds. It is not intended that the present invention be limited to the nature of the salt. In one embodiment, said N-aminopyridinium salt has the . In one embodiment, said N- aminopyridinium salt has the structure: 4-6 are independently selected from an aryl group or H. In one embodi pyridinium salt has the structure: . In one embodiment, said unactivated alkene has the , alkyl or substituted alkyl or H; R2is an alkyl or substituted alkyl is an alkyl or substituted alkyl or H. In one embodiment, said unactivated alkene comprises an alkene without an electron-withdrawing group directly attached to the double bond. In one embodiment, said unactivated alkene comprises a gaseous olefin. In one embodiment, said pyridinium aziridine compound has the , wherein R1 is an alkyl or substituted alkyl or H; R2 is an alkyl or substituted is an alkyl or substituted alkyl or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said pyridinium aziridine compound is selected from the group consisting of:

[0002] N pyMe py N py N pyMN N pyn n= 1 2 4e In comprises iodosylbenzene. In one embodiment, said hypervalent iodine reagent comprises an iminoiodinane. In one embodiment, the invention relates to a method of cross coupling a pyridinium aziridine comprising; a) providing; i) a pyridinium aziridine compound; ii) an aryl boronic acid; b) reacting said pyridinium aziridine compound with said aryl boronic acid so as create an aryl- aziridine compound. In one embodiment, said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or H; R2 is an alkyl or substituted alkyl or an alkyl or substituted alkyl or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said aryl boronic acid has the structure . In one embodiment, said aryl boronic acid is selected from the gro sisting of: . said aryl-aziridine compound has the structure: , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substituted alkyl is an alkyl or substituted alkyl or H. In one embodiment, said aryl-aziridine compound has the structure selected from the group consisting of:

[0003] . n one emo men, e nven on reaes o a me o o reuc ve epyr ya on of pyridinium aziridine compound comprising; a) providing; i) said pyridinium aziridine compound; ii) ammonium chloride; and iii) zinc; b) exposing said pyridinium aziridine compound with said ammonium chloride and zinc so as create an N-H-aziridine compound. In one embodiment, said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or H; R2is an alkyl or substituted is an alkyl or substituted alkyl or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said aryl- aziridine compound has the structure selected from the group consisting of:

[0004] . In one embodiment, said N-H-aziridine compound has the , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substituted R3is an alkyl or substituted alkyl or H. In one embodiment, the invention relates to a method comprising; a) providing; i) a compound comprising a clickable aryl aziridine probe; ii) protein; b) reacting said protein with said clickable aryl aziridine probe so as to create a compound-bound protein; c) capturing said compound-bound protein using a click-chemistry compatible structure. In one embodiment, said protein comprises at least one aspartate or glutamate residues. In one embodiment, said compound- bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein. In one embodiment, said clickable aryl aziridine probe has the structure: e embodiment, said click-chemistry compatible structure comprises a ne embodiment, capturing comprising reacting a compound comprising a terminal alkyne group with a terminal azide group. In one embodiment, the method further comprises step d) determining the identity of compound-bound proteins. In one embodiment, the method further comprises step d) determining the structure of compound-bound proteins. In one embodiment, determining the identity comprises identification of said protein with mass spectrometry. In one embodiment, the invention relates to a method comprising; a) providing; i) an aryl aziridine probe; ii) a protein, wherein said protein is a catalyst; b) reacting said protein with said clickable aryl aziridine probe so as to create a compound-bound protein; and c) measuring the catalytic activity of said compound-bound protein. In one embodiment, the method further comprises step d) determining if said catalytic activity of said compound-bound protein is inhibited compared to the catalytic activity of unbound protein. In one embodiment, the method further comprises step d) comparing the catalytic activity of said compound-bound protein at various concentrations. In one embodiment, the method further comprises step d) comparing the catalytic activity of said compound-bound protein to the catalytic activity of compound-bound protein produced by exposure of said protein to a different aryl aziridine probe. In one embodiment, said aryl-aziridine probe has the structure: , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substituted alkyl or is an alkyl or substituted alkyl or or H. In one embodiment, said protein comprises at least one aspartate or glutamate residues. In one embodiment, said compound-bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein. In one embodiment, said aryl aziridine probe comprises a clickable aryl aziridine probe. In one embodiment, the invention relates to a method of olefin activation in the dark (i.e. without the need for light) comprising; a) providing; i) an N-aminopyridinium salt; ii) at least one unactivated alkene; and iii) a hypervalent iodine reagent; and b) reacting said unactivated alkene with said N-aminopyridinium in the presence of said hypervalent iodine reagent so as create a pyridinium aziridine compound. In one embodiment, said N-aminopyridinium salt has the structure: . In one embodiment, said method is metal free. In one embodiment, said In one embodiment, said N-aminopyridinium salt has the structure: 6 are independently selected from an aryl group or H. In one embodiment, said N-aminopyridinium salt has the . In one embodiment, said unactivated alkene has the , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such as allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, said unactivated alkene comprises an alkene without an electron-withdrawing group directly attached to the double bond. In one embodiment, said unactivated alkene comprises a gaseous olefin. In one embodiment, said pyridinium aziridine compound has the , wherein R1is an alkyl or substituted alkyl or the like (i.e. other groups such as allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said pyridinium aziridine compound is selected from the group consisting of:

[0005] N pyMepy N pyMeN py N N pyn n= 1 2 4. In reagent comprises iodosylbenzene. In one embodiment, said hypervalent iodine reagent comprises an iminoiodinane. In one embodiment, the invention relates to a method of cross coupling a pyridinium aziridine comprising; a) providing; i) a pyridinium aziridine compound; ii) an aryl boronic acid; b) reacting said pyridinium aziridine compound with said aryl boronic acid so as create an aryl-aziridine compound. In one embodiment, said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such as methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said aryl boronic acid has the . In one embodiment, said aryl boronic acid is selected from the of: . said aryl-aziridine compound has the structure: , wherein R1is an alkyl or substituted alkyl or the like (i.e. other groups such as allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, said aryl-aziridine compound has the structure selected from the group consisting of:

[0006] . n one em o men , e me o ur er compr ses a re uc ve epyr ya on o sa pyr nium aziridine compound comprising; a) providing; i) said pyridinium aziridine compound; ii) ammonium chloride; and iii) zinc; b) exposing said pyridinium aziridine compound with said ammonium chloride and zinc so as create an N-H-aziridine compound. In one embodiment, said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said aryl-aziridine compound has the structure selected from the group consisting of: . In one embodiment, said N-H-aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, the method further comprises a method of cross coupling a pyridinium aziridine comprising; a) providing; i) a pyridinium aziridine compound; ii) an aryl boronic acid; b) reacting said pyridinium aziridine compound with said aryl boronic acid so as create an aryl-aziridine compound. In one embodiment, said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such as allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said aryl boronic acid has the In one embodiment, said aryl boronic acid is selected from consisting of: . said aryl-aziridine compound has the structure: , wherein R1is an alkyl or substituted alkyl or the like (i.e. other groups such as alka thyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, said aryl-aziridine compound has the structure selected from the group consisting of: . one to a of pyridinium aziridine compound comprising; a) providing; i) said pyridinium aziridine compound; ii) ammonium chloride; and iii) zinc; b) exposing said pyridinium aziridine compound with said ammonium chloride and zinc so as create an N-H-aziridine compound. In one embodiment, said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R4-6are independently selected from an aryl group or H. In one embodiment, said aryl-aziridine compound has the structure selected from the group consisting of:

[0007] . In one embodiment, said N-H-aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, the invention relates to a method comprising; a) providing; i) a compound comprising a clickable aryl aziridine probe; ii) protein; b) reacting said protein with said clickable aryl aziridine probe so as to create a compound-bound protein; c) capturing said compound-bound protein using a click-chemistry compatible structure. In one embodiment, said protein comprises at least one aspartate or glutamate residue. In one embodiment, said compound- bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein. In one embodiment, said clickable aryl aziridine probe has the structure: one embodiment, said click-chemistry compatible structure comprises a In one embodiment, capturing comprising reacting a compound comprising a terminal alkyne group with a terminal azide group. In one embodiment, the method further comprises step d) determining the identity of compound-bound proteins. In one embodiment, the method further comprises step d) determining the structure of said compound-bound protein. In one embodiment, identifying comprises determining the identity of said protein with mass spectrometry. In one embodiment, the invention relates to a method comprising; a) providing; i) an aryl aziridine probe; ii) a protein, wherein said protein is a catalyst; b) reacting said protein with said clickable aryl aziridine probe so as to create a compound-bound protein; and c) measuring the catalytic activity of said compound-bound protein. In one embodiment, step d) determining if said catalytic activity of said compound-bound protein is inhibited compared to the catalytic activity of unbound protein. In one embodiment, the method further comprises step d) comparing the catalytic activity of said compound-bound protein at various concentrations. In one embodiment, the method further comprises step d) comparing the catalytic activity of said compound-bound protein to the catalytic activity of compound-bound protein produced by exposure of said protein to a different aryl aziridine probe. In one embodiment, said aryl-aziridine probe has the structure: , wherein R1is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, said aryl aziridine probe comprises a clickable aryl aziridine probe. In one embodiment, said aryl aziridine probe reacts with a residue of said protein to produce said compound-bound protein. In one embodiment, said residue is a catalytic residue. In one embodiment, said residue is a non-catalytic residue. In one embodiment, said protein comprises at least one aspartate or glutamate residues. In one embodiment, said compound-bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein. In one embodiment, said aspartate or glutamate residues are catalytic glutamic and aspartic acid residues. In one embodiment, said aspartate or glutamate residues are non-catalytic glutamic and aspartic acid residues. In one embodiment, said protein is a catalyst.. In one embodiment, said protein is an enzyme. In one embodiment, said protein is a transcription factor. In one embodiment, said protein is an antibody. In one embodiment, said protein is a hormone. In one embodiment, said protein is a membrane protein. In one embodiment, said protein is a receptor. In one embodiment, said protein is a structural protein. In one embodiment, said protein is a transport protein. In one embodiment, said protein is a fibrous protein. In one embodiment, said protein is a storage protein. In one embodiment, the invention relates to a method comprising; a) providing; i) an aziridine probe; ii) a protein; b) reacting said protein with said aziridine probe so as to create a compound-bound protein; and c) measuring activity associated with said protein. In one embodiment, step d) determining if said activity of said compound-bound protein is altered compared to the activity associated with said unbound protein. In one embodiment, the method further comprises step d) comparing the activity associated with said unbound protein with the activity of said compound-bound protein at various concentrations. In one embodiment, said aziridine probe comprises an aryl aziridine probe. In one embodiment, said aryl aziridine probe comprises a clickable aryl aziridine probe. In one embodiment, said protein is a catalyst.. In one embodiment, said protein is an enzyme. In one embodiment, said protein is a transcription factor. In one embodiment, said protein is an antibody. In one embodiment, said protein is a hormone. In one embodiment, said protein is a membrane protein. In one embodiment, said protein is a receptor. In one embodiment, said protein is a structural protein. In one embodiment, said protein is a transport protein. In one embodiment, said protein is a fibrous protein. In one embodiment, said protein is a storage protein. In one embodiment, the method further comprises step d) comparing the activity associated with said unbound protein of said compound-bound protein to the associated activity of compound-bound protein produced by exposure of said protein to a different aryl aziridine probe. In one embodiment, said aryl-aziridine probe has the , wherein R1is an alkyl or substituted alkyl or the like (i.e. other groups such as allyl, cyclopropyl, or a substituted version of any of these groups) or H; R2is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H; and R3is an alkyl or substituted alkyl or the like (i.e. other groups such as alkanediyl, methyl, allyl, cyclopropyl, or a substituted version of any of these groups) or H. In one embodiment, said protein comprises at least one aspartate or glutamate residues. In one embodiment, said compound-bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein. In one embodiment, said aspartate or glutamate residues are catalytic glutamic and aspartic acid residues. In one embodiment, said aspartate or glutamate residues are non-catalytic glutamic and aspartic acid residues. In one embodiment, the invention relates to a method of N-aziridinyl radical transfer comprising; a) providing; i) an olefin compound; ii) an unsubstituted N-pyridinium aziridine; b) reacting said olefin compound with said unsubstituted N-pyridinium aziridine so as create an hydroxyazirdine compound. In one embodiment, said unsubstituted N-pyridinium aziridine compound has the structure: , wherein R1 is an aryl or substituted aryl; R2 is an aryl, substituted aryl, or H; R3is an alkyl or substituted alkyl or H; and R4-8are independently selected from an aryl, substituted aryl, alkyl, substituted alkyl, halogen, bridging group or H. In one embodiment, said unsubstituted N-pyridinium aziridine compound has the structure: 8 are independently selected from an aryl, substituted aryl, alkyl, group or H. In one embodiment, said reacting further comprises a photocatalyst. In one embodiment, said reacting further comprises this use of LiBr. In one embodiment, said reacting further comprises this use of Et3N. In one embodiment, said olefin has the structure: one embodiment, said hydroxyazirdine compound is selected from the following:

[0008] . 5 DEFINITIONS To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims. As utilized herein, it should be understood that “click-chemistry compatible” structures, functional groups, monomers, oligomers, etc., refer to compounds, materials, etc. that are structurally characterized by including one or more chemical moieties suitable for participation in a click-chemistry reaction. In embodiments where copper-catalyzed azide-alkyne cycloaddition (CuAAC) is the click-chemistry employed for functionalizing materials as disclosed herein, the “click-chemistry compatible” compounds include a terminal alkyne and / or terminal azide functional group. The exemplary and preferred click-chemistry reaction described herein is CuAAC, although skilled artisans will appreciate that other click-chemistry compatible reactions that would be appreciated as equivalent to CuAAC upon reading these descriptions may be employed without departing from the scope of the inventive concepts described herein. For instance, in various embodiments click-chemistry compatible reactions may include CuAAC, strain- promoted azide-alkyne cycloaddition (SPAAC), strain-promoted alkyne-nitrone cycloaddition (SPANC), strained alkene reactions such as alkene-azide cycloaddition, etc. Click-chemistry compatible reactions may also be considered to include alkene-tetrazine inverse-demand Diers- Alder reactions, alkene-tetrazole photoclick reactions, Michael additions of thiols, nucleophilic substitution of thiols with amines, and certain Diels-Alder reactions, etc. such as disclosed by Becer, et al. “Click chemistry beyond metal-catalyzed cycloaddition.”Angew. Chem. Int. Ed. 2009, 48: p.4900-4908 [1], and equivalents thereof as would be understood by a person having ordinary skill in the art upon reading the present disclosures. Accordingly, click-chemistry compatible groups, compounds, etc. should be understood to include one or more suitable chemical moieties conveying capability to participate in any combination of the foregoing exemplary click chemistries, in various embodiments. For the groups below, the following parenthetical subscripts further define the groups as follows: “(Cn)” defines the exact number (n) of carbon atoms in the group; “(C^n)” defines the maximum number (n) of carbon atoms that can be in the group; (Cn-n′) defines both the minimum (n) and maximum number (n′) of carbon atoms in the group. For example, “alkoxy(C^10)” designates those alkoxy groups having from 1 to 10 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, or any range derivable therein (e.g., 3-10 carbon atoms)). Similarly, “alkyl(C2-10)” designates those alkyl groups having from 2 to 10 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10, or any range derivable therein (e.g., 3-10 carbon atoms)). The term “alkyl” when used without the “substituted” modifier refers to a non-aromatic monovalent group with a saturated carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The groups, −CH3(Me), −CH2CH3(Et), −CH2CH2CH3(n-Pr), −CH(CH3)2(iso-Pr), −CH(CH2)2(cyclopropyl), −CH2CH2CH2CH3(n-Bu), −CH(CH3)CH2CH3(sec-butyl), −CH2CH(CH3)2(iso-butyl), −C(CH3)3(tert-butyl), −CH2C(CH3)3(neo-pentyl), cyclobutyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl are non-limiting examples of alkyl groups. The term “substituted alkyl” refers to a non-aromatic monovalent group with a saturated carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The following groups are non-limiting examples of substituted alkyl groups: −CH2OH, −CH2Cl, −CH2Br, −CH2SH, −CF3, −CH2CN, −CH2C(O)H, −CH2C(O)OH, −CH2C(O)OCH3, −CH2C(O)NH2, −CH2C(O)NHCH3, −CH2C(O)CH3, −CH2OCH3, −CH2OCH2CF3, −CH2OC(O)CH3, −CH2NH2, −CH2NHCH3, −CH2N(CH3)2, −CH2CH2Cl, −CH2CH2OH, −CH2CF3, −CH2CH2OC(O)CH3, −CH2CH2NHCO2C(CH3)3, and −CH2Si(CH3)3. The term “alkanediyl” when used without the “substituted” modifier refers to a non- aromatic divalent group, wherein the alkanediyl group is attached with two ^-bonds, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The groups, −CH2− (methylene), −CH2CH2−, −CH2C(CH3)2CH2−, −CH2CH2CH2−, and , are non-limiting examples of alkanediyl groups. The term “substituted alkanediyl” aromatic monovalent group, wherein the alkynediyl group is attached with two ^- bonds, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The following groups are non-limiting examples of substituted alkanediyl groups: −CH(F)−, −CF2−, −CH(Cl)−, −CH(OH)−, −CH(OCH3)−, and −CH2CH(Cl)−. The term “alkenyl” when used without the “substituted” modifier refers to a monovalent group with a nonaromatic carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. Non-limiting examples of alkenyl groups include: −CH=CH2(vinyl), −CH=CHCH3, −CH=CHCH2CH3, −CH2CH=CH2(allyl), −CH2CH=CHCH3, and −CH=CH−C6H5. The term “substituted alkenyl” refers to a monovalent group with a nonaromatic carbon atom as the point of attachment, at least one nonaromatic carbon- carbon double bond, no carbon-carbon triple bonds, a linear or branched, cyclo, cyclic or acyclic structure, and at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The groups, −CH=CHF, −CH=CHCl and −CH=CHBr, are non-limiting examples of substituted alkenyl groups. The term “alkenediyl” when used without the “substituted” modifier refers to a non- aromatic divalent group, wherein the alkenediyl group is attached with two ^-bonds, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. The groups, −CH=CH−, −CH=C(CH3)CH2−, −CH=CHCH2−, and , are non-limiting examples of alkenediyl groups. The term “substituted to a non-aromatic divalent group, wherein the alkenediyl group is attached with two ^-bonds, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The following groups are non-limiting examples of substituted alkenediyl groups: −CF=CH−, −C(OH)=CH−, and −CH2CH=C(Cl)−. The term “alkynyl” when used without the “substituted” modifier refers to a monovalent group with a nonaromatic carbon atom as the point of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen. The groups, −C≡CH, −C≡CCH3, −C≡CC6H5and −CH2C≡CCH3, are non-limiting examples of alkynyl groups. The term “substituted alkynyl” refers to a monovalent group with a nonaromatic carbon atom as the point of attachment and at least one carbon-carbon triple bond, a linear or branched, cyclo, cyclic or acyclic structure, and at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The group, −C≡CSi(CH3)3, is a non- limiting example of a substituted alkynyl group. The term “alkynediyl” when used without the “substituted” modifier refers to a non- aromatic divalent group, wherein the alkynediyl group is attached with two ^-bonds, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen. The groups, −C≡C−, −C≡CCH2−, and −C≡CCH(CH3)− are non-limiting examples of alkynediyl groups. The term “substituted alkynediyl” refers to a non-aromatic divalent group, wherein the alkynediyl group is attached with two ^-bonds, with two carbon atoms as points of attachment, a linear or branched, cyclo, cyclic or acyclic structure, at least one carbon-carbon triple bond, and at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The groups −C≡CCFH− and −C≡CHCH(Cl)− are non-limiting examples of substituted alkynediyl groups. The term “aryl” when used without the “substituted” modifier refers to a monovalent group with an aromatic carbon atom as the point of attachment, said carbon atom forming part of a six- membered aromatic ring structure wherein the ring atoms are all carbon, and wherein the monovalent group consists of no atoms other than carbon and hydrogen. Non-limiting examples of aryl groups include phenyl (Ph), methylphenyl, (dimethyl)phenyl, −C6H4CH2CH3(ethylphenyl), −C6H4CH2CH2CH3(propylphenyl), −C6H4CH(CH3)2, −C6H4CH(CH2)2, −C6H3(CH3)CH2CH3(methylethylphenyl), −C6H4CH=CH2(vinylphenyl), −C6H4CH=CHCH3, −C6H4C≡CH, −C6H4C≡CCH3, naphthyl, and the monovalent group derived from biphenyl. The term “substituted aryl” refers to a monovalent group with an aromatic carbon atom as the point of attachment, said carbon atom forming part of a six-membered aromatic ring structure wherein the ring atoms are all carbon, and wherein the monovalent group further has at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. Non-limiting examples of substituted aryl groups include the groups: −C6H4F, −C6H4Cl, −C6H4Br, −C6H4I, −C6H4OH, −C6H4OCH3, −C6H4OCH2CH3, −C6H4OC(O)CH3, −C6H4NH2, −C6H4NHCH3, −C6H4N(CH3)2, −C6H4CH2OH, −C6H4CH2OC(O)CH3, −C6H4CH2NH2, −C6H4CF3, −C6H4CN, −C6H4CHO, −C6H4CHO, −C6H4C(O)CH3, −C6H4C(O)C6H5, −C6H4CO2H, −C6H4CO2CH3, −C6H4CONH2, −C6H4CONHCH3, and −C6H4CON(CH3)2. The term “arenediyl” when used without the “substituted” modifier refers to a divalent group, wherein the arenediyl group is attached with two ^-bonds, with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic ring structure(s) wherein the ring atoms are all carbon, and wherein the monovalent group consists of no atoms other than carbon and hydrogen. Non-limiting examples of arenediyl groups include: . the arenediyl group is attached with two ^-bonds, with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic rings structure(s), wherein the ring atoms are all carbon, and wherein the divalent group further has at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The term “aralkyl” when used without the “substituted” modifier refers to the monovalent group −alkanediyl−aryl, in which the terms alkanediyl and aryl are each used in a manner consistent with the definitions provided above. Non-limiting examples of aralkyls are: phenylmethyl (benzyl, Bn), 1-phenyl-ethyl, 2-phenyl-ethyl, indenyl and 2,3-dihydro-indenyl, provided that indenyl and 2,3-dihydro-indenyl are only examples of aralkyl in so far as the point of attachment in each case is one of the saturated carbon atoms. When the term “aralkyl” is used with the “substituted” modifier, either one or both the alkanediyl and the aryl is substituted. Non- limiting examples of substituted aralkyls are: (3-chlorophenyl)-methyl, 2-oxo-2-phenyl-ethyl (phenylcarbonylmethyl), 2-chloro-2-phenyl-ethyl, chromanyl where the point of attachment is one of the saturated carbon atoms, and tetrahydroquinolinyl where the point of attachment is one of the saturated atoms. The term “heteroaryl” when used without the “substituted” modifier refers to a monovalent group with an aromatic carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom forming part of an aromatic ring structure wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the monovalent group consists of no atoms other than carbon, hydrogen, aromatic nitrogen, aromatic oxygen and aromatic sulfur. Non-limiting examples of aryl groups include acridinyl, furanyl, imidazoimidazolyl, imidazopyrazolyl, imidazopyridinyl, imidazopyrimidinyl, indolyl, indazolinyl, methylpyridyl, oxazolyl, phenylimidazolyl, pyridyl, pyrrolyl, pyrimidyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, tetrahydroquinolinyl, thienyl, triazinyl, pyrrolopyridinyl, pyrrolopyrimidinyl, pyrrolopyrazinyl, pyrrolotriazinyl, pyrroloimidazolyl, chromenyl (where the point of attachment is one of the aromatic atoms), and chromanyl (where the point of attachment is one of the aromatic atoms). The term “substituted heteroaryl” refers to a monovalent group with an aromatic carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom forming part of an aromatic ring structure wherein at least one of the ring atoms is nitrogen, oxygen or sulfur, and wherein the monovalent group further has at least one atom independently selected from the group consisting of non- aromatic nitrogen, non-aromatic oxygen, non-aromatic sulfur F, Cl, Br, I, Si, and P. The term “heteroarenediyl” when used without the “substituted” modifier refers to a divalent group, wherein the heteroarenediyl group is attached with two ^-bonds, with an aromatic carbon atom or nitrogen atom as the point of attachment, said carbon atom or nitrogen atom two aromatic atoms as points of attachment, said carbon atoms forming part of one or more six- membered aromatic ring structure(s) wherein the ring atoms are all carbon, and wherein the monovalent group consists of no atoms other than carbon and hydrogen. Non-limiting examples of heteroarenediyl groups . The term “substituted wherein the heteroarenediyl group is attached with two ^-bonds, with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic rings structure(s), wherein the ring atoms are all carbon, and wherein the divalent group further has at least one atom independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The term “heteroaralkyl” when used without the “substituted” modifier refers to the monovalent group −alkanediyl−heteroaryl, in which the terms alkanediyl and heteroaryl are each used in a manner consistent with the definitions provided above. Non-limiting examples of aralkyls are: pyridylmethyl, and thienylmethyl. When the term “heteroaralkyl” is used with the “substituted” modifier, either one or both the alkanediyl and the heteroaryl is substituted. The term “acyl” when used without the “substituted” modifier refers to a monovalent group with a carbon atom of a carbonyl group as the point of attachment, further having a linear or branched, cyclo, cyclic or acyclic structure, further having no additional atoms that are not carbon or hydrogen, beyond the oxygen atom of the carbonyl group. The groups, −CHO, −C(O)CH3, −C(O)CH2CH3, −C(O)CH2CH2CH3, −C(O)CH(CH3)2, −C(O)CH(CH2)2, −C(O)C6H5, −C(O)C6H4CH3, −C(O)C6H4CH2CH3, −COC6H3(CH3)2, and −C(O)CH2C6H5, are non-limiting examples of acyl groups. The term “acyl” therefore encompasses, but is not limited to groups sometimes referred to as “alkyl carbonyl” and “aryl carbonyl” groups. The term “substituted acyl” refers to a monovalent group with a carbon atom of a carbonyl group as the point of attachment, further having a linear or branched, cyclo, cyclic or acyclic structure, further having at least one atom, in addition to the oxygen of the carbonyl group, independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The groups, −C(O)CH2CF3, −CO2H (carboxyl), −CO2CH3(methylcarboxyl), −CO2CH2CH3, −CO2CH2CH2CH3, −CO2C6H5, −CO2CH(CH3)2, −CO2CH(CH2)2, −C(O)NH2(carbamoyl), −C(O)NHCH3, −C(O)NHCH2CH3, −CONHCH(CH3)2, −CONHCH(CH2)2, −CON(CH3)2, −CONHCH2CF3, −CO−pyridyl, −CO−imidazoyl, and −C(O)N3, are non-limiting examples of substituted acyl groups. The term “substituted acyl” encompasses, but is not limited to, “heteroaryl carbonyl” groups. The term “alkylidene” when used without the “substituted” modifier refers to the divalent group =CRR′, wherein the alkylidene group is attached with one ^-bond and one ^-bond, in which R and R′ are independently hydrogen, alkyl, or R and R′ are taken together to represent alkanediyl. Non-limiting examples of alkylidene groups include: =CH2, =CH(CH2CH3), and =C(CH3)2. The term “substituted alkylidene” refers to the group =CRR′, wherein the alkylidene group is attached with one ^-bond and one ^-bond, in which R and R′ are independently hydrogen, alkyl, substituted alkyl, or R and R′ are taken together to represent a substituted alkanediyl, provided that either one of R and R′ is a substituted alkyl or R and R′ are taken together to represent a substituted alkanediyl. The term “alkoxy” when used without the “substituted” modifier refers to the group −OR, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkoxy groups include: −OCH3, −OCH2CH3, −OCH2CH2CH3, −OCH(CH3)2, −OCH(CH2)2, −O−cyclopentyl, and −O−cyclohexyl. The term “substituted alkoxy” refers to the group −OR, in which R is a substituted alkyl, as that term is defined above. For example, −OCH2CF3is a substituted alkoxy group. Similarly, the terms “alkenyloxy”, “alkynyloxy”, “aryloxy”, “aralkoxy”, “heteroaryloxy”, “heteroaralkoxy” and “acyloxy”, when used without the “substituted” modifier, refers to groups, defined as −OR, in which R is alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and acyl, respectively, as those terms are defined above. When any of the terms alkenyloxy, alkynyloxy, aryloxy, aralkyloxy and acyloxy is modified by “substituted,” it refers to the group −OR, in which R is substituted alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and acyl, respectively. The term “alkylamino” when used without the “substituted” modifier refers to the group −NHR, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkylamino groups include: −NHCH3, −NHCH2CH3, −NHCH2CH2CH3, −NHCH(CH3)2, −NHCH(CH2)2, −NHCH2CH2CH2CH3, −NHCH(CH3)CH2CH3, −NHCH2CH(CH3)2, −NHC(CH3)3, −NH−cyclopentyl, and −NH−cyclohexyl. The term “substituted alkylamino” refers to the group −NHR, in which R is a substituted alkyl, as that term is defined above. For example, −NHCH2CF3is a substituted alkylamino group. The term “dialkylamino” when used without the “substituted” modifier refers to the group −NRR′, in which R and R′ can be the same or different alkyl groups, or R and R′ can be taken together to represent an alkanediyl having two or more saturated carbon atoms, at least two of which are attached to the nitrogen atom. Non-limiting examples of dialkylamino groups include: −NHC(CH3)3, −N(CH3)CH2CH3, −N(CH2CH3)2, N-pyrrolidinyl, and N-piperidinyl. The term “substituted dialkylamino” refers to the group −NRR′, in which R and R′ can be the same or different substituted alkyl groups, one of R or R′ is an alkyl and the other is a substituted alkyl, or R and R′ can be taken together to represent a substituted alkanediyl with two or more saturated carbon atoms, at least two of which are attached to the nitrogen atom. The terms “alkoxyamino”, “alkenylamino”, “alkynylamino”, “arylamino”, “aralkylamino”, “heteroarylamino”, “heteroaralkylamino”, and “alkylsulfonylamino” when used without the “substituted” modifier, refers to groups, defined as −NHR, in which R is alkoxy, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and alkylsulfonyl, respectively, as those terms are defined above. A non-limiting example of an arylamino group is −NHC6H5. When any of the terms alkoxyamino, alkenylamino, alkynylamino, arylamino, aralkylamino, heteroarylamino, heteroaralkylamino and alkylsulfonylamino is modified by “substituted,” it refers to the group −NHR, in which R is substituted alkoxy, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and alkylsulfonyl, respectively. The term “amido” (acylamino), when used without the “substituted” modifier, refers to the group −NHR, in which R is acyl, as that term is defined above. A non-limiting example of an acylamino group is −NHC(O)CH3. When the term amido is used with the “substituted” modifier, it refers to groups, defined as −NHR, in which R is substituted acyl, as that term is defined above. The groups −NHC(O)OCH3and −NHC(O)NHCH3are non-limiting examples of substituted amido groups. The term “alkylimino” when used without the “substituted” modifier refers to the group =NR, wherein the alkylimino group is attached with one ^-bond and one ^-bond, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkylimino groups include: =NCH3, =NCH2CH3and =N−cyclohexyl. The term “substituted alkylimino” refers to the group =NR, wherein the alkylimino group is attached with one ^-bond and one ^-bond, in which R is a substituted alkyl, as that term is defined above. For example, =NCH2CF3is a substituted alkylimino group. Similarly, the terms “alkenylimino”, “alkynylimino”, “arylimino”, “aralkylimino”, “heteroarylimino”, “heteroaralkylimino” and “acylimino”, when used without the “substituted” modifier, refers to groups, defined as =NR, wherein the alkylimino group is attached with one ^- bond and one ^-bond, in which R is alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and acyl, respectively, as those terms are defined above. When any of the terms alkenylimino, alkynylimino, arylimino, aralkylimino and acylimino is modified by “substituted,” it refers to the group =NR, wherein the alkylimino group is attached with one ^-bond and one ^-bond, in which R is substituted alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and acyl, respectively. The term “alkylthio” when used without the “substituted” modifier refers to the group −SR, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkylthio groups include: −SCH3, −SCH2CH3, −SCH2CH2CH3, −SCH(CH3)2, −SCH(CH2)2, −S−cyclopentyl, and −S−cyclohexyl. The term “substituted alkylthio” refers to the group −SR, in which R is a substituted alkyl, as that term is defined above. For example, −SCH2CF3is a substituted alkylthio group. Similarly, the terms “alkenylthio”, “alkynylthio”, “arylthio”, “aralkylthio”, “heteroarylthio”, “heteroaralkylthio”, and “acylthio”, when used without the “substituted” modifier, refers to groups, defined as −SR, in which R is alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and acyl, respectively, as those terms are defined above. When any of the terms alkenylthio, alkynylthio, arylthio, aralkylthio, heteroarylthio, heteroaralkylthio, and acylthio is modified by “substituted,” it refers to the group −SR, in which R is substituted alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heteroaralkyl and acyl, respectively. The term “thioacyl” when used without the “substituted” modifier refers to a monovalent group with a carbon atom of a thiocarbonyl group as the point of attachment, further having a linear or branched, cyclo, cyclic or acyclic structure, further having no additional atoms that are not carbon or hydrogen, beyond the sulfur atom of the carbonyl group. The groups, −CHS, −C(S)CH3, −C(S)CH2CH3, −C(S)CH2CH2CH3, −C(S)CH(CH3)2, −C(S)CH(CH2)2, −C(S)C6H5, −C(S)C6H4CH3, −C(S)C6H4CH2CH3, −C(S)C6H3(CH3)2, and −C(S)CH2C6H5, are non-limiting examples of thioacyl groups. The term “thioacyl” therefore encompasses, but is not limited to, groups sometimes referred to as “alkyl thiocarbonyl” and “aryl thiocarbonyl” groups. The term “substituted thioacyl” refers to a radical with a carbon atom as the point of attachment, the carbon atom being part of a thiocarbonyl group, further having a linear or branched, cyclo, cyclic or acyclic structure, further having at least one atom, in addition to the sulfur atom of the carbonyl group, independently selected from the group consisting of N, O, F, Cl, Br, I, Si, P, and S. The groups, −C(S)CH2CF3, −C(S)O2H, −C(S)OCH3, −C(S)OCH2CH3, −C(S)OCH2CH2CH3, −C(S)OC6H5, −C(S)OCH(CH3)2, −C(S)OCH(CH2)2, −C(S)NH2, and −C(S)NHCH3, are non- limiting examples of substituted thioacyl groups. The term “substituted thioacyl” encompasses, but is not limited to, “heteroaryl thiocarbonyl” groups. The term “alkylsulfonyl” when used without the “substituted” modifier refers to the group −S(O)2R, in which R is an alkyl, as that term is defined above. Non-limiting examples of alkylsulfonyl groups include: −S(O)2CH3, −S(O)2CH2CH3, −S(O)2CH2CH2CH3, −S(O)2CH(CH3)2, −S(O)2CH(CH2)2, −S(O)2−cyclopentyl, and −S(O)2−cyclohexyl. The term “substituted alkylsulfonyl” refers to the group −S(O)2R, in which R is a substituted alkyl, as that term is defined above. For example, −S(O)2CH2CF3is a substituted alkylsulfonyl group. Similarly, the terms “alkenylsulfonyl”, “alkynylsulfonyl”, “arylsulfonyl”, “aralkylsulfonyl”, “heteroarylsulfonyl”, and “heteroaralkylsulfonyl” when used without the “substituted” modifier, refers to groups, defined as −S(O)2R, in which R is alkenyl, alkynyl, aryl, aralkyl, heteroaryl, and heteroaralkyl, respectively, as those terms are defined above. When any of the terms alkenylsulfonyl, alkynylsulfonyl, arylsulfonyl, aralkylsulfonyl, heteroarylsulfonyl, and heteroaralkylsulfonyl is modified by “substituted,” it refers to the group −S(O)2R, in which R is substituted alkenyl, alkynyl, aryl, aralkyl, heteroaryl and heteroaralkyl, respectively. The term “alkylammonium” when used without the “substituted” modifier refers to a group, defined as −NH2R+, −NHRR′+, or −NRR′R′′+, in which R, R′ and R′′ are the same or different alkyl groups, or any combination of two of R, R′ and R′′ can be taken together to represent an alkanediyl. Non-limiting examples of alkylammonium cation groups include: −NH2(CH3)+, −NH2(CH2CH3)+, −NH2(CH2CH2CH3)+, −NH(CH3)2+, −NH(CH2CH3)2+, −NH(CH2CH2CH3)2+, −N(CH3)3+, −N(CH3)(CH2CH3)2+, −N(CH3)2(CH2CH3)+, −NH2C(CH3)3+, −NH(cyclopentyl)2+, and −NH2(cyclohexyl)+. The term “substituted alkylammonium” refers −NH2R+, −NHRR′+, or −NRR′R′′+, in which at least one of R, R′ and R′′ is a substituted alkyl or two of R, R′ and R′′ can be taken together to represent a substituted alkanediyl. When more than one of R, R′ and R′′ is a substituted alkyl, they can be the same of different. Any of R, R′ and R′′ that are not either substituted alkyl or substituted alkanediyl, can be either alkyl, either the same or different, or can be taken together to represent a alkanediyl with two or more carbon atoms, at least two of which are attached to the nitrogen atom shown in the formula. The term “alkylsulfonium” when used without the “substituted” modifier refers to the group −SRR′+, in which R and R′ can be the same or different alkyl groups, or R and R′ can be taken together to represent an alkanediyl. Non-limiting examples of alkylsulfonium groups include: −SH(CH3)+, −SH(CH2CH3)+, −SH(CH2CH2CH3)+, −S(CH3)2+, −S(CH2CH3)2+, −S(CH2CH2CH3)2+, −SH(cyclopentyl)+, and −SH(cyclohexyl)+. The term “substituted alkylsulfonium” refers to the group −SRR′+, in which R and R′ can be the same or different substituted alkyl groups, one of R or R′ is an alkyl and the other is a substituted alkyl, or R and R′ can be taken together to represent a substituted alkanediyl. For example, −SH(CH2CF3)+is a substituted alkylsulfonium group. The term “alkylsilyl” when used without the “substituted” modifier refers to a monovalent group, defined as −SiH2R, −SiHRR′, or −SiRR′R′′, in which R, R′ and R′′ can be the same or different alkyl groups, or any combination of two of R, R′ and R′′ can be taken together to represent an alkanediyl. The groups, −SiH2CH3, −SiH(CH3)2, −Si(CH3)3and −Si(CH3)2C(CH3)3, are non- limiting examples of unsubstituted alkylsilyl groups. The term “substituted alkylsilyl” refers −SiH2R, −SiHRR′, or −SiRR′R′′, in which at least one of R, R′ and R′′ is a substituted alkyl or two of R, R′ and R′′ can be taken together to represent a substituted alkanediyl. When more than one of R, R′ and R′′ is a substituted alkyl, they can be the same of different. Any of R, R′ and R′′ that are not either substituted alkyl or substituted alkanediyl, can be either alkyl, either the same or different, or can be taken together to represent an alkanediyl with two or more saturated carbon atoms, at least two of which are attached to the silicon atom. In addition, atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms. Isotopes, as used herein, include those atoms having the same atomic number but different mass numbers. By way of general example and without limitation, isotopes of hydrogen include tritium and deuterium, and isotopes of carbon include13C and14C. Similarly, it is contemplated that one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s). Furthermore, it is contemplated that one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s). A compound having a formula that is represented with a dashed bond is intended to include the formulae optionally having zero, one or more double bonds. Thus, for example, the structure includes the structures , , , and . As will be understood by a person of skill in the art, no one such ring atom forms part of more than one double bond. Any undefined valency on an atom of a structure shown in this application implicitly represents a hydrogen atom bonded to the atom. A ring structure shown with an unconnected “R” group, indicates that any implicit hydrogen atom on that ring can be replaced with that R group. In the case of a divalent R group (e.g., oxo, amino, thio, alkylidene, etc.), any pair of implicit hydrogen atoms attached to one atom of that ring can be replaced by that R group. This concept is as exemplified below:.As used her roup that is capable of influencing the stereoselectivity of a reaction. Persons of skill in the art are familiar with such compounds, and many are commercially available. The term “protecting group,” as that term is used in the specification and / or claims, is used in the conventional chemical sense as a group, which reversibly renders unreactive a functional group under certain conditions of a desired reaction and is understood not to be H. After the desired reaction, protecting groups may be removed to deprotect the protected functional group. All protecting groups should be removable (and hence, labile) under conditions which do not degrade a substantial proportion of the molecules being synthesized. In contrast to a protecting group, a “capping group” permanently binds to a segment of a molecule to prevent any further chemical transformation of that segment. It should be noted that the functionality protected by the protecting group may or may not be a part of what is referred to as the protecting group. Protecting groups include but are not limited to: Alcohol protecting groups: Acetoxy group, β-Methoxyethoxymethyl ether (MEM), methoxymethyl ether (MOM), p-methoxybenzyl ether (PMB), methylthiomethyl ether, pivaloyl (Piv), tetrahydropyran (THP), silyl ethers (including but not limited to trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), and triisopropylsilyl (TIPS) ethers), methyl ethers, and ethoxyethyl ethers (EE). Amine protecting groups: carbobenzyloxy (Cbz) group, p-methoxybenzyl carbonyl (Moz or MeOZ) group, tert-butyloxycarbonyl (BOC) group, 9-fluorenylmethyloxycarbonyl (FMOC) group, benzyl (Bn) group, p-methoxybenzyl (PMB), dimethoxybenzyl (DMPM), p-methoxyphenyl (PMP) group, tosyl (Ts) group, and other sulfonamides (Nosyl & Nps) groups. Carbonyl protecting groups: acetals, ketals, acylals, and dithianes. Carboxylic acid protecting groups: alkyl esters, aryl esters, silyl esters. Protection of terminal alkynes protected as propargyl alcohols in the Favorskii reaction. The term “leaving group,” as that term is used in the specification and / or claims, is an atom or group (charged or uncharged) that becomes detached from an atom in what is considered to be the residual or main part of the substrate in a specified reaction. Leaving groups include, but are not limited to: NH2−( amine), CH3O−(methoxy), HO−(hydroxyl), CH3COO−(carboxylate), H2O (water), F−, Cl−, Br−, I−, N3−(azide), SCN−(thiocyanate), NO2(nitro), and protecting groups. The use of the word “a” or “an,” when used in conjunction with the term “comprising” in the claims and / or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects. The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,” “comprising,” “has,” “having,” “includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps. The term “effective,” as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result. The term “hydrate” when used as a modifier to a compound means that the compound has less than one (e.g., hemihydrate), one (e.g., monohydrate), or more than one (e.g., dihydrate) water molecules associated with each compound molecule, such as in solid forms of the compound. An “isomer” of a first compound is a separate compound in which each molecule contains the same constituent atoms as the first compound, but where the configuration of those atoms in three dimensions differs. As used herein, “predominantly one enantiomer” means that a compound contains at least about 85% of one enantiomer, or more preferably at least about 90% of one enantiomer, or even more preferably at least about 95% of one enantiomer, or most preferably at least about 99% of one enantiomer. Similarly, the phrase “substantially free from other optical isomers” means that the composition contains at most about 15% of another enantiomer or diastereomer, more preferably at most about 10% of another enantiomer or diastereomer, even more preferably at most about 5% of another enantiomer or diastereomer, and most preferably at most about 1% of another enantiomer or diastereomer. “Prevention” or “preventing” includes: (1) inhibiting the onset of a disease in a subject or patient which may be at risk and / or predisposed to the disease but does not yet experience or display any or all of the pathology or symptomatology of the disease, and / or (2) slowing the onset of the pathology or symptomatology of a disease in a subject or patient which may be at risk and / or predisposed to the disease but does not yet experience or display any or all of the pathology or symptomatology of the disease. “Prodrug” means a compound that is convertible in vivo metabolically into an inhibitor according to the present invention. The prodrug itself may or may not also have activity with respect to a given protein. For example, a compound comprising a hydroxy group may be administered as an ester that is converted by hydrolysis in vivo to the hydroxy compound. Suitable esters that may be converted in vivo into hydroxy compounds include acetates, citrates, lactates, phosphates, tartrates, malonates, oxalates, salicylates, propionates, succinates, fumarates, maleates, methylene-bis-^-hydroxynaphthoate, gentisates, isethionates, di-p-toluoyltartrates, methane-sulfonates, ethanesulfonates, benzenesulfonates, p-toluenesulfonates, cyclohexyl- sulfamates, quinates, esters of amino acids, and the like. Similarly, a compound comprising an amine group may be administered as an amide that is converted by hydrolysis in vivo to the amine compound. The term “saturated” when referring to an atom means that the atom is connected to other atoms only by means of single bonds. A “stereoisomer” or “optical isomer” is an isomer of a given compound in which the same atoms are bonded to the same other atoms, but where the configuration of those atoms in three dimensions differs. “Enantiomers” are stereoisomers of a given compound that are mirror images of each other, like left and right hands. “Diastereomers” are stereoisomers of a given compound that are not enantiomers. Enantiomers are compounds that individually have properties said to have “optical activity” and consist of chiral molecules. If a chiral molecule is dextrorotary, its enantiomer will be levorotary, and vice-versa. In fact, the enantiomers will rotate polarized light the same number of degrees, but in opposite directions. “Dextrorotation” and “levorotation” (also spelled laevorotation) refer, respectively, to the properties of rotating plane polarized light clockwise (for dextrorotation) or counterclockwise (for levorotation). A compound with dextrorotation is called “dextrorotary,” while a compound with levorotation is called “levorotary”. A standard measure of the degree to which a compound is dextrorotary or levorotary is the quantity called the “specific rotation” “[α]”. Dextrorotary compounds have a positive specific rotation, while levorotary compounds have negative. Two enantiomers have equal and opposite specific rotations. A dextrorotary compound is prefixed “(+)-” or “d-”. Likewise, a levorotary compound is often prefixed “(-)-” or “l-”. These “d-” and “l-” prefixes should not be confused with the “D-” and “L-” based on the actual configuration of each enantiomer, with the version synthesized from naturally occurring (+)-compound being considered the D- form. A mixture of enantiomers of the compounds is prefixed “(±)-”. An equal mixture of enantiomers of the compounds is considered “optically inactive”. In addition, atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms. Isotopes, as used herein, include those atoms having the same atomic number but different mass numbers. By way of general example and without limitation, isotopes of hydrogen include tritium and deuterium, and isotopes of carbon include13C and14C. Similarly, it is contemplated that one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s). Furthermore, it is contemplated that one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s). In structures wherein stereochemistry is not explicitly indicated, it is assumed that all stereochemistry is considered and all isomers claimed. In structures where the specific isomers or enantiomers are indicated, the specific enantiomer is claimed. Any undefined valency on an atom of a structure shown in this application implicitly represents a hydrogen atom bonded to the atom. Bonds to copper (Cu) metal may be coordinate bonds and are not necessarily considered covalent. In a specific embodiment, the term "pharmaceutically acceptable" means approved by a regulatory agency of the federal or a state government or listed in the U.S. Pharmacopeia or other generally recognized pharmacopeia for use in animals, and more particularly in humans. The term "carrier" refers to a diluent, adjuvant, excipient or vehicle with which the active compound is administered. Such pharmaceutical vehicles can be liquids, such as water and oils, including those of petroleum, animal, vegetable or synthetic origin, such as peanut oil, soybean oil, mineral oil, sesame oil and the like. The pharmaceutical vehicles can be saline, gum acacia, gelatin, starch paste, talc, keratin, colloidal silica, urea, and the like. In addition, auxiliary, stabilizing, thickening, lubricating and coloring agents can be used. When administered to a subject, the pharmaceutically acceptable vehicles are preferably sterile. Water can be the vehicle when the active compound is administered intravenously. Saline solutions and aqueous dextrose and glycerol solutions can also be employed as liquid vehicles, particularly for injectable solutions. Suitable pharmaceutical vehicles also include excipients such as starch, glucose, lactose, sucrose, gelatin, malt, rice, flour, chalk, silica gel, sodium stearate, glycerol monostearate, talc, sodium chloride, dried skim milk, glycerol, propylene glycol, water, ethanol and the like. The present compositions, if desired, can also contain minor amounts of wetting or emulsifying agents, or pH buffering agents. Pharmaceutically acceptable sugars include but are not limited to sucrose, dextrose, maltose, galactose, rhamnose, and lactose. Pharmaceutically acceptable sugar alcohols include but are not limited to mannitol, xylitol, and sorbitol. As used herein, the term “iminoiodinane” is used throughout the specification to describe an example of a hypervalent iodine compound. As used herein, the term “unactivated alkene” is used throughout the specification to describe an alkene without an electron-withdrawing group directly attached to the double bond. BRIEF DESCRIPTION OF THE DRAWINGS The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. The accompanying figures, which are incorporated into and form a part of the specification, illustrate several embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The figures are only for the purpose of illustrating a preferred embodiment of the invention and are not to be construed as limiting the invention. FIG.1 shows various aziridine-containing natural products and drugs. FIG. 2 shows a two-step synthesis method previously developed that enables rapid generation of diverse N-aryl aziridine fragments through triphenyl pyridinium (TPP) aziridine intermediates. FIG.3 shows an envisioned three step process wherein 1) click chemistry is used to help capture then 2) determine the identity of proteins that react with aziridine compounds and 3) subsequently optimize aziridine compounds for optimal reaction or inhibition with a target protein. FIG.4 shows an DNA damaging assay in HCT116 colorectal cancer cells with two example compounds, mitomycin C (MMC), which targets genomic DNA, TPP fragment phenyl aziridine (PA) (N-aryl azirdine 2b) show no signal for DNA damage marker y2AX. Phenyl aziridine shows no DNA damage in live cancer cells. FIG.5 shows one synthetic path to produce chemoproteomic probe 1. FIG.6 shows an in-gel fluorescence scan of chemoproteomic probe 1 labeling in HCT116 colorectal cancer cells. FIG.7 shows fluorescence microscopy images of 1-labeled proteins in HCT116 cells with the same probe was shown to target proteins in the cytosol a nucleus of HCT116 cells. FIG.8 shows a potential mechanism of aziridine reacting with proteins. FIG.9 shows that majority of the aziridine adducts were found to be adducts of glutamate or aspartate residues. FIG.10 shows a representative MS2 spectrum of an aziridine adduct. FIG. 11 shows the observed selectivity of probe 1 is also shown in a preferential modification of aspartic (D) and glutamic (E) acids in human proteomes. FIG.12 shows that probe 1 preferentially modifies proteins in the cytosol and nucleus. FIG.13 shows the amnio acid distribution of hepta peptides enriched by probe 1. FIG.14 shows the type of amino acids in peptides enriched by probe 1. FIG.15 shows a pathway analysis that indicated functional clustering of probe 1-modified proteins, particularly showing those with fatty acid derivative binding, fatty-acyl-CoA binding, and thiolester hydrolase activity. FIG.16 shows in-gel profiling of N-substituted aziridine targets. FIG. 17 shows selected protein enriched by 3 µM of probe 1 in situ in a comparison of proteins competed by fragment versus Log2 (competitor / DMSO), wherein blue bands in the heatmap to the left indicate target proteins. The darker the shade, the stronger the competition. FIG. 18 shows target proteins for each compound (1a-1g) are shown as grey dots below the dashed line. The trend on the number of targets again corresponded to the heatmap of FIG.17. FIG.19 shows results that electron withdrawing groups enhance the reactivity of aziridines of compounds 1a-1g. FIG. 20 shows hits clustering per compound (1a-1g), wherein selected proteins (brown circle) can be targeted by moderately reactive aziridines and the subcellular distribution of the hits, which indicates that target proteins are enriched in the cytosol, ER, and nucleus. FIG.21 shows selected biomedically relevant hits and their competition ratios. FIG. 22 shows that controlling N-substitution is challenging for many aziridination reactions: N-aryl aziridines are intrinsically challenging molecules to access with existing molecules. FIG. 23 shows existing aziridination methods which were largely limited to specific N- functional groups and to activated (aromatic) olefin substrates. FIG.24A shows that most bioactive aziridines reported so far can be seen as arising from unactivated olefins, while FIG.24B shows that methods for olefin aziridination put more emphasis on making activated aziridines from activated olefins. In contrast to FIG. 24C shows previously reported iodide catalyzed aziridination of styrenes with N-amionopyridinium, here FIG.24D the present invention reports a metal free aziridination of unactivated olefins. FIG.25 shows selected optimization efforts for olefin aziridination. FIG. 26 shows iodosylbenzene-mediated aziridination. Condition: 2 (1.0 equiv., 0.30 mmol), 3 (1.0 equiv.), PhI=O (4, 2.0 equiv.). (aPrepared on 1.0 mmol scale with respect to 2;bUsing CH3CN as the solvent;cIsolated as a mixture of trans- and cis- aziridine.) FIG.27 shows Pyridinium aziridines 5 derived from unactivated alkenes participate in a) nickel catalyzed cross-coupling for synthesis of N-aryl aziridines; and b) deaminative reduction to give free N–H aziridines followed by N-protection. Condition: 5 (1.0 equiv, 0.10–0.20 mmol), 11 (2.4 equiv), Ni(phen)Br2(20 mol%), 2,4,6-collidine (1.0 equiv). Deprotection: 5 (0.20 mmol, 1.0 equiv), I2(5.0 mol%), Zn (10 equiv), NH4Cl (10 equiv). a) TsCl, K2CO3, DMAP (10 mol%), 23 °C. b): Boc2O, Et3N, CH2Cl2, 0 to 23 °C. FIG.28 shows the synthesis of 1-aminopyridin-1-ium trifluoromethanesulfonate. FIG.29 shows the synthesis of N-pyridinium Aziridines from Vinyl Arenes. FIG. 30 shows additional examples of Fully-functionalized aryl pyridinium aziridine fragments, including those which are from para-substitution, meta-substitution, and ortho- substitution. FIG.31 shows fully-functionalized linear pyridinium aziridine fragments. FIG.32 show a selection of diverse pyridinium aziridine fragments that competed with the probe 1. FIG.32 shows an in-gel profiling of diverse TPP ligand targets using probe 1 to compete selected probe 1-labeled bands in live cells. FIG.33 show a selection of diverse pyridinium aziridine fragments that competed with the probe 1. FIG.33 shows an in-gel profiling of diverse TPP ligand targets using probe 1 to compete selected 1-labeled bands in live cells. FIG.34 show a selection of diverse pyridinium aziridine fragments that competed with the probe 1. FIG.34 shows an in-gel profiling of diverse TPP ligand targets using probe 1 to compete selected probe 1-labeled bands in live cells. FIG. 35shows the structure of variousN-aminopyridinium 2,4,6-trimethylbenzenesulfonates. FIG.36 shows the structures of various aliphatic olefins. FIG.37 shows the structures of various products of aziridination of aliphatic olefins. FIG.38 shows structures of exemplary products of cross-coupling of pyridinium aziridines. FIG.39 shows structures of exemplary products of depyridylation of pyridinium aziridines. FIG.40 shows structures of exemplary iodosylbenzene derivatives. FIG.41 shows structures of non-limiting problematic olefin substrates for the aziridination method of the current invention. FIG.42A shows selected aziridine-containing natural products. FIG.42B shows classical synthetic disconnections for aziridines and N-functionalization chemistry. FIG. 42C shows one embodiment of the present invention, the synthesis and reactivity of N-aziridinyl radicals, which engage in intermolecular olefin addition chemistry. PC = photocatalyst. FIG. 43 shows conditions: 102 (0.1 mmol), 104 (0.15 mmol), Et3N (0.2 mmol), Ir(ppy)3(1.0 mol%), LiBr (0.1 mmol), blue LED irradiation at 23 ºC in MeCN:H2O (1:1, 2.0 mL).b0.2 mL CH2Cl2was added as the olefin 104n is sparingly soluble in MeCN. Isolated yields. FIG.44A shows Conditions: 106 (0.1 mmol), 104 (0.15 mmol), Et3N (0.2 mmol), Ir(ppy)3 (1.0 mol%), LiBr (0.1 mmol), blue LED irradiation at 23 ºC in MeCN:H2O (1:1, 2.0 mL).b0.2 mL CH2Cl2was added as the olefin 104p was sparingly soluble in MeCN. Isolated yields. FIG.44B shows unsubstituted aziridine was engaged into photocatalytic reaction to get hydroxyazirinated product 109 involving simplest aziridinyl radical. A shows Conditions: 106 (0.1 mmol), 104 (0.15 mmol), Et3N (0.2 mmol), Ir(ppy)3(1.0 mol%), LiBr (0.1 mmol), blue LED irradiation at 23 ºC in MeCN:H2O (1:1, 2.0 mL).b0.2 mL CH2Cl2was added as the olefin 104p was sparingly soluble in MeCN. Isolated yields. B shows unsubstituted aziridine was engaged into photocatalytic reaction to get hydroxyazirinated product 9 involving simplest aziridinyl radical. FIG.46 shows potential photocatalytic mechanism for N-aziridinyl radical generation and transfer. FIG.47 shows aziridine group transfer via N-aziridinyl radical. FIG.48 shows various hydroxyaziridination products. FIG.49 shows various azabicyclo-ol products. FIG. 50 shows a1H NMR spectrum of addition elimination product 103 in CDCl3(400 MHz) at 23 ^C. FIG. 51 shows the EPR spectra for photochemically generated aziridinyl radical in the presence of PBN was obtained in CH3CN : (—) Experimental spectrum and (—) simulated spectrum. FIG.52 shows HRMS data for radical clock reaction. Both the hydroxy-azirinated and ring opened product 110 were observed. FIG.53A&B shows emission spectra. FIG.53A shows Emission spectrum of solution of Ir(ppy)3(8.4 × 10-5M) with different concentrations of 102a in MeCN under N2atmosphere at 20 ℃. (—) 0.0 mM, (—) 0.69 mM, (—) 1.03 mM, (—) 1.30 mM, (—) 2.07 mM, and (—) 2.70 mM. FIG. 53B shows Emission spectrum of solution of PC (8.4 × 10-5M) with different concentrations of Et3N in MeCN under N2atmosphere at 20 ℃. (—) 0.0 mM, (—) 0.69 mM, (—) 1.03 mM, (—) 1.30 mM, and (—)2.70 mM. FIG. 54 shows a Stern-Volmer plot in the quenching study of PC using 102a or Et3N inCH2Cl2 under N2 atmosphere at 20 ℃ with emission wavelength fixed at 515 nm. Plot ofemission intensity ratio using 102a (—) and liner fit (×) vs.102a concentration (R2= 0.91); plot of emission intensity ratio using Et3N (—) and linear fit (×) vs. Et3N concentration (R2= 0.78). FIG. 55A-D shows cyclic voltammograms. FIG. 55A shows a cyclic voltammogram of dissolved molecular oxygen in MeCN. FIG.55B shows a cyclic voltammogram of 2,4,6-triphenyl- 1-(2-phenylaziridin-1-yl)pyridin-1-ium (102a) under ambient conditions. FIG.55C shows a cyclic voltammogram of 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1-ium (102a) under a nitrogen atmosphere. FIG.55D shows an overlay of the CV data from parts FIG.55 B and FIG.55C. CV conditions: substrate 5.00 mM, 0.200 M [TBA]PF6solution of CH3CN, glassy carbon working electrode, Pt counter electrode, and scan rate = 0.10 V / s. FIG.56 shows displacement ellipsoid plot of 105v plotted at 50% probability. H-atoms are removed for clarity. The crystalline sample used for the diffraction experiment was obtained via pentane diffusion into EtOAc. FIG. 57 shows a Displacement ellipsoid plot of 108 plotted at 50% probability. H-atoms are removed for clarity. The crystalline sample used for the diffraction experiment was obtained via diethylether diffusion into CH3CN. For clarity only one molecule in the unit cell is depicted here. DETAILED DESCRIPTON OF THE INVENTION The present invention provides a suite of pyridinium aziridine and aryl aziridine compounds as covalent, aspartate- and glutamate-reactive protein inhibitors and a method for synthesizing these compounds and subsequently identifying their protein targets. The method comprises 1) reacting molecules containing an olefin moiety with an N-aminopyridinium reagent to produce the pyridinium aziridine compounds. The corresponding aryl aziridines can be subsequently obtained by a one-step cross-coupling reaction of pyridinium aziridines with diverse boronic acids. 2) capturing and identifying compound-bound target proteins using a "clickable" aryl aziridine probe and mass spectrometry-based chemical proteomics. In summary, the present invention provides methods for synthesis, target identification, and biological evaluation of a novel class of chemical compounds for covalent targeting of aspartate and glutamate residues on disease relevant proteins to expand the scope of the currently accessible druggable proteome. One of the major challenges in modern drug discovery lies in the fact that only a relatively small subset of disease-relevant proteins can currently be effectively targeted by small molecule drugs. This limitation arises due to the specific molecular structures and properties required for successful drug-protein interactions. Many proteins lack accessible binding sites or exhibit complex structures that hinder the development of drugs capable of interacting with them in a therapeutically beneficial manner. Consequently, this constraint reduces the pool of druggable protein targets, limiting the scope for creating novel pharmaceutical interventions to address various diseases and medical conditions. In one embodiment, the present invention describes a new class of molecules that significantly expands the available druggable targets by targeting carboxylic acid residues that have so far remained untargetable. Covalent targeting of otherwise undruggable proteins presents a promising solution to the challenge of limited drug targets. Unlike traditional drug development approaches that rely on non- covalent interactions, covalent targeting forms strong and enduring bonds between drugs and proteins. This allows for a broader range of proteins, including those with elusive binding sites or intricate structures, to be effectively engaged. The covalent approach enhances the likelihood of developing therapeutically viable drugs by providing a more versatile and comprehensive strategy for addressing a wider array of disease-associated proteins. Specifically, the present invention approach involves the development of N-pyridinium aziridines and N-aryl aziridines as a new scaffold of covalent inhibitors to selectively target aspartic and glutamic acid residues on proteins that are otherwise considered undruggable. Consequently, this technology will expand the scope of available drug targets, offering new opportunities for therapeutic development. The aziridine group is a key component in various bio-active natural products and drug molecules, see FIG.1. FDA-approved oncology therapies like mitomycin C and thiotepa feature the aziridine core component. Aziridines as covalent inhibitors and their proteomic target landscape have not yet been systematically studied. Synthetically accessing structurally-diverse aziridines and exploring their protein targets holds promise for discovering novel covalent drug candidates. The existing strategies to address the limited druggable target problem through covalent chemistry primarily focus on the development of cysteine-, serine- and lysine-directed covalent inhibitors. The herein presented N-pyridinium aziridines and N-aryl aziridines offer the opportunity to target aspartic acid and glutamic acid residues on proteins, herewith expanding the range of targetable amino acid residues on proteins. Previously reported two-step synthesis method enables rapid generation of diverse N-aryl aziridine fragments through triphenyl pyridinium (TPP) aziridine intermediates [2], see FIG. 2. Chemical proteomics studies enable target ID and prioritization of high-value TPP fragments, which are accessed from commercial substrates in a single chemical step, see FIG.3. Converting selected hit TPP fragments to corresponding aryl aziridines as one-step optimization to develop potent and selective covalent inhibitors. It was found that, in contrast with mitomycin C (MMC), which targets genomic DNA, phenyl aziridine fragment (PA) (N-aryl azirdine 2b) show no signal for DNA damage marker y2AX. See FIG.4. Phenyl aziridine shows no DNA damage in live cancer cells. Characterizing protein reactivity of aryl aziridine probe: It was found that use of a chemoproteomic probe , showed the ability to modify proteins in living cancer cells. produce chemoproteomic probe 1. FIG.6 shows an in-gel fluorescence scan of chemoproteomic probe 1 labeling in HCT116 colorectal cancer cells. Stars (*) indicate proteins preferentially labeled by probe 1 at lower concentrations. Probe 1 covalently modifies proteins in live cancer cells. This same probe was shown to target proteins in the cytosol and nucleus of HCT116 cells, see Fluorescence microscopy images of 1- labeled proteins in HCT116 cells in FIG.7. The identity of the type of aziridine adduct was studied using chemical proteomics. Although it is not necessary to understand the mechanism of an invention, it is believed that the mechanism of aziridine reacting with proteins is illustrated in FIG. 8. Cells were treated with probe 1 and the resulting mass adducts were detected through mass spectrometry. It was found that the majority of the aziridine adducts were found to be adducts of glutamate or aspartate residues, as shown in FIG. 9. FIG. 10 provides a representative MS2 spectrum of an aziridine adduct. The MS2 fragmentation confirms the structure of the azirdine adduct. This selectivity of probe 1 is also shown in a preferential modification of aspartic (D) and glutamic (E) acids in human proteomes, see FIG. 11. Further, it was found that probe 1 preferentially modifies proteins in the cytosol and nucleus, see FIG. 12. Additionally, FIG. 13 shows the amnio acid distribution of hepta peptides enriched by probe 1. FIG.14 shows the type of amino acids in peptides enriched by probe 1. These results indicate that probe 1 binds to protein regions enriched in hydrophobic residues. Pathway analysis in FIG. 15 reveals functional clustering of probe 1-modified proteins, particularly showing those with fatty acid derivative binding, fatty-acyl-CoA binding, and thiolester hydrolase activity. Table 1 shows selected biomedically relevant probe 1-modified proteins with their respective sites of binding. In one embodiment, the present invention describes tuning of reactivity and selectivity through N- substitution of the probe 1 in new probes 1a-1g as shown in FIG.16. FIG.16 shows in-gel profiling of N-substituted aziridine targets. HCT116 cells were pretreated with 10 µM of the indicated competitor, and then followed by post-labeling with 3 µM of 1. Bands with decreased intensities (*) are the targets of each corresponding competitor. Although it is not necessary to understand the mechanism of an invention, it is believed that distinct target profiles can by achieved by varying the N-substitution. Varying R groups at the N-substituted position enables binding and competition of different proteins (indicated by the stars *). Further, it was found that varying R groups at the N-substituted position also alters the number of targets of each compound, which is suggestive of specificity. FIG.17 shows selected protein enriched by 3 µM of probe 1 in situ in a comparison of proteins competed by the indicated fragments, wherein blue bands in the heatmap to the left indicate target proteins. The darker the shade, the stronger the competition. In FIG.18, target proteins enriched by probe 1 for each compound (1a-1g) are shown as grey dots below the dashed line. The trend on the number of targets again corresponded to the heatmap of FIG. 17. Further, FIG.19 indicates that electron withdrawing groups enhance the reactivity of aziridines of compounds 1a-1g. FIG.20 shows hits clustering per compound (1a-1g), wherein selected proteins (brown circle) can be targeted by moderately reactive aziridines and the subcellular distribution of the hits, which indicates that target proteins are enriched in the cytosol, ER, and nucleus. FIG.21 shows selected biomedically relevant hits and their competition ratios. Table 1: Selected biomedically relevant probe 1-modified proteins with their respective sites of binding as indicated with *. Gene Name Protein Name Modified Sequence SEQ ID NO: In contrast to epoxide synthesis, aziridine synthesis continues to present significant synthetic challenges, see FIG.22. Controlling N-substitution is challenging for many aziridination reactions: N-aryl aziridines are intrinsically challenging molecules to access with existing molecules. FIG. 30 shows additional examples of fully-functionalized aryl pyridinium aziridine fragments, including those which are from para-substitution, meta-substitution, and ortho- substitution. FIG. 31 shows fully-functionalized linear pyridinium aziridine fragments. FIG. 32 show a selection of diverse pyridinium aziridine fragments that competed with the probe 1. FIG. 32 shows an in-gel profiling of diverse TPP ligand targets using probe 1 to compete selected probe 1-labeled bands in live cells. FIG.33 show a selection of diverse pyridinium aziridine fragments that competed with the probe 1. FIG. 33 shows an in-gel profiling of diverse TPP ligand targets using probe 1 to compete selected 1-labeled bands in live cells. FIG.34 show a selection of diverse pyridinium aziridine fragments that competed with the probe 1. FIG.34 shows an in-gel profiling of diverse TPP ligand targets using probe 1 to compete selected probe 1-labeled bands in live cells. Chemical synthesis of pyridinium aziridines The chemical innovation that enabled discovery of these new molecular platforms is the development of pyridinium aziridines and the demonstration that these molecules engage in modular synthetic derivatization. The previous efforts had the only previous art in the synthesis of pyridinium aziridines [2]. This disclosure describes for the first-time new methods that significantly expand the scope of aziridine molecules that are available (novel molecular targets) and the simple diversification of these scaffolds. To address this challenge, an aziridination protocol with a complementary alkene substrate scope is described herein. Kinetic studies and mass spectrometric data suggested in situ  formation of reactive iminoiodinane 1 which took part in catalyst-free olefin activation in the dark, in contrast to widely studied metal catalyzed or photoinduced alkene aziridination withiminoiodinanes (e.g.,  PhINTs). Instead of free-nitrene insertion, mechanistic experiments hinttowards a carbocation intermediate responsible for aziridine formation. Aziridines play an important role as both synthetic targets and key intermediates present in pharmaceuticals and natural products. A catalyst-free aziridination of unactivated alkenes with N-aminopyridinium salt facilitated by hypervalent iodine reagent is described. This method features mild reaction condition, a wide substrate scope, and good chemoselectivity. Moreover, the aziridination of unactivated alkenes with N-aminopyridinium salt is not visible- light-induced. It is not photocatalyzed. As a result, it can be done in the dark, i.e. in the absence of light or without the need for light. The obtained pyridinium aziridines participate in Ni- catalyzed cross-coupling to afford N-aryl aziridines. Preliminary data indicates a transient iminoiodanane to be responsible for substrate activation. Experimental evidence suggests a cationic pathway during aziridination with iminoiodinane. Together, these results represent the synthetic utility of pyridinium aziridines as synthons for diversified C–N bond formation. Moreover, mechanistic observations provide unprecedented insights into the catalyst-free alkene activation with iminoiodinane. Owing to the nucleophilic ring-opening reactivity, aziridines are capable of many regio- and stereoselective transformations, recognized as simple but important N-heterocycleswith great synthetic interest [3-5]. While a rare moiety in natural products, aziridines havemaintained research interest as they represent the major bioactive functional group for everyaziridine-containing natural product discovered so far [6-8]. Due to their unique properties,aziridines have shown potential as electrophilic “warheads” for pharmaceutical applications. Thus, intense research efforts have been dedicated to aziridine chemistry to develop various aziridination methods. Retrosynthetically, aziridines can be envisioned as arising from a nitrene equivalent with an olefinic substrate. As a result, olefin activation has prevailed in aziridine synthesis, with the advantage of olefins being versatile and abundant in natural products and industrial chemicals. In fact, alkenes represent the second most prevalent functional group in naturalproducts [7]. Metal-catalyzed aziridination with activated alkenes (e.g., vinyl arenes or α,β-unsaturated carbonyl compounds) has been widely reported, typically using iminoiodinane orazides as the electrophilic nitrogen source [9-11]. Recent progress has also seen metal-freeaziridination; however, these methods are often limited to styrenes, and are much less applied to unactivated alkenes. Besides, styrenic aziridines do not represent nature occurring aziridineswhich are classicallysynthesized via azide ring-opening of epoxide, followed by treatment withPPh3. While a handfulof methods have described the aziridination of aliphatic alkenes, particularsubstrates such as di- or trisubstituted alkenes remain challenging [12-16]. On the other hand,activated N-substituted aziridines (N-sulfonyl, N-acyl) have been much more investigated because the corresponding nitrene precursors are more stable and readily available. However, the N-protecting groups require additional steps before derivatization to other functionalities is possible. Therefore, access to unactivated aziridines (NH, N-alkyl, N-aryl) is less explored and remains synthetically attractive

[0017] . N-substituted pyridinium salts have been widely utilized as key precursors in bothpyridine and alkene functionalization [18-25]. N-aminopyridinium salts represent a potent classof nitrogen group transfer reagents which utilize both a nucleophilic N-amino group and a low- lying pyridinium- centered LUMO that allows access to N-centered radicals. N-aminopyridinum salts were envisioned as a potential nitrene precursor for alkene aziridination, from which the pyridinium aziridine could be easily converted to unactivated aziridines. Based on this, it has previously been demonstrated the synthesis of pyridinium aziridine from vinyl arenes, followed by cross-coupling for the synthesis of N-aryl aziridines; however, aziridination with unactivated olefins was inefficient. Alkene aziridination. The previously reported N-pyridinium aziridine synthesis relied on iodide-catalyzed olefin activation and was limited to styrenyl substrates, presumably due to the need for benzylic stabilization of radical intermediates. It was hypothesized that a broader scope of olefins could participate in direct aziridination chemistry if a reagent were available for the direct transfer of a pyridinium nitrene fragment (i.e., py–N). To this end, N-pyridinium iminoiodinane reagents was targeted based on the expected electrophilicity of a hypervalent iodine compound bearing a cationic pyridinium moiety. The aziridination of cyclohexene with N- aminopyridinium 3 was investigated as a model reaction, and an optimized condition was found using excess iodosylbenzene 4 in hexafluoroisopropanol (HFIP) as the solvent. Control reactions indicated using excess 4 was important (Table 2, entries 1, 2 and 3) to achieving efficient aziridination with the olefin as the limiting reagent. Solvent choice was also important: While reactions in HFIP typically gives 5a in higher yields than in MeCN, a mixed solvent system resulted in decreased yield (Table 2, entry 4). Metal salts that are often utilized in aziridination catalysis, such as AgOTf, had no significant impact on aziridination efficiency (Table 2, entry 5). See Examples for additional optimization details. Equiv 2a Equiv 4 Solvent Additive Yielda1 1 2 HFIP --- 99% ons were carried out on 0.20 mmol scale with respect to 3.aYields were determined by 1,3,5- trimethoxybenzene as the standard. FIG.26 depicts the array of aliphatic alkenes that participate in efficient aziridination. Cyclic alkenes (cyclohexene, cyclopentene, cyclooctene and 3-carene) engaged in efficient aziridination to afford pyridinium aziridines 5a to 5d, respectively. Five- and six-membered aziridines are formed with exclusively cis-stereochemistry. For 8-membered cyclic alkenes, formation of both cis- and trans-aziridines (c-5c : t-5c = 6.25 : 1.00) is observed based on thecoupling constants of the aziridine-derived 1 H NMR resonances. The cis-isomer c-5c couldbe isolated at analytical purity. Assignment of cis- / trans- mixtures was bolstered by aziridination with 1,5-cyclooctadiene 5f, which afforded a 1.0 : 1.0 c-5f : t-5f mixture. The trans- stereochemistry of t-5f was confirmed by single-crystal X-ray diffraction. Norbornene undergoes exo-aziridination to afford 5e in 69% yield; the stereochemistry of aziridination was confirmed by single-crystal X-ray diffraction following cross coupling (vide infra). Terminal alkenes with different functional groups including alkyl halide, ester, nitrile and azide underwent aziridination with good yield (5g to 5p). N- Heterocycles were tolerated as demonstrated in the aziridination of 2q. With 4-vinyl homoallylbenzene 2r, aziridination occurred at the styrenic C=C bond. Pharmaceutical derivatives containing aliphatic alkenes were synthesized and were also subjected to aziridination, including derivatives of ibuprofen 2s, oxaprozin 2t and celecoxib 2u. The corresponding aziridines (5s, 5t, and 5u) were obtained in moderate yields. Natural product derivatives containing olefins, including geraniol, β-caryophyllene 1x, dehydroepiandrosterone 2y, and R-carvone 2z also engage in efficient aziridination. For geraniol derivatives, aziridination selectively occurred at the C=C bond further away from the functional group (5v and 5w). For β- caryophyllene, aziridination occurred at the endocyclic C=C bond (5x), and in R-carvone, aziridination exclusively occurred at the more unactivated C=C bond (5z). During aziridination, formation of imine was also observed as a side reaction for some substrates (e.g., carvone, celecoxib derivative). In the case of carvone, the imine byproduct (5z’) could be isolated in analytical purity in 18% yield. Gaseous alkenes also participated in aziridination. Aziridination with ethylene gas occurred at 2 atm in moderate yield, affording aziridine product 5 which coeluted with pyridinium imine 5’ as the by product. Aziridination with propylene as well as isobutylene was carried out in a similar fashion, affording a mixture of aziridine (5ab and 5ac) and imine in moderate yields. With access to a large family of N-pyridinium aziridines, the viability of the C–N cross- coupling chemistry was investigated similarly to methods previously developed in the context of styrene- derived aziridines. In short, Ni-catalyzed cross-coupling of N-pyridinium aziridines with aryl boronic acids does provide entry to N-arylaziridines, although the efficiency is highly structure dependent. Simple pyridinium aziridines 5a and 5q underwent cross-coupling in moderate yields (FIG. 27). Norbornene-derived aziridine 5e cross-coupled with 3,5- bis(trifluoromethyl)phenyl boronic acid 11a to give the N-aryl aziridine 12c; single-crystal X- ray diffraction confirmed the observed exo-stereochemistry. Pharmaceutical / natural product derivatives of pyridinium aziridines 5 as well as boronic acids 11 could cross-couple with each other to form complex N-aryl aziridines 12 (FIG. 27). For example, pyridinium aziridines derived from geranyl acetate, β-caryophyllene, and dehydroepiandrosterone (5v, 5x, and 5y) were cross-coupled with 3,5-bis(trifluoromethyl)phenyl boronic acid 11a, affording N-aryl aziridines in moderate to good yields. Stereochemistry of 12f was also confirmed by single-crystal X-ray diffraction. Indomethacin derived boronic acid 11b could also be cross-coupled with pyridinium aziridine 5e in moderate yield (12g). While N-aryl aziridines (12h and 12i) were obtained from celecoxib and carvone derivatives (5u and 5z), the cross-coupling was not as efficient. Finally, cross-coupling between dehydroepiandrosterone derived pyridinium aziridine 5y and indomethacin derived boronic acid 11b was carried out to afford a complex N-aryl aziridine 12j in 23% yield. In addition to Ni-catalyzed Suzuki-type cross-coupling, pyridinium aziridines 5 could be deprotected to release the free N–H aziridines 13 under relatively mild reducing conditions (FIG. 27). For example, deprotection of 5e with Zn metal resulted in N–H aziridine 13a withquantitative NMRyield. For ease of isolation, the obtained 13a was subjected to TsCl in onepot, or Boc2O aftersolvent swap, to afford the protected aziridines 14 and 15 in good yields.Pyridinium aziridines derived from geranyl acetate and β-caryophyllene (5v and 5x) underwent deprotection smoothly to afford the corresponding aziridines 13b and 13c in moderate isolated yields (FIG.27). In summary, the aziridination of unactivated alkenes with N-aminopyridinium salt is described. The obtained pyridinium aziridine features N-activation by pyridinium that can be easily derivatized. The present invention showcases the utility of pyridinium aziridine by nickel- catalyzed cross-coupling. Mechanistic study indicated iminoiodanane might have been involved in aziridination. These studies provide a broader substrate scope for formal nitrene transfer strategy via pyridinium aziridine. The aziridines made by the present invention may be used in organic synthesis. They may be used as synthons. They may for example be used in the synthesis of a pharmaceutical product or in the synthesis of a natural product or in the synthesis of a veterinary product. They may be N-substituted aziridines. They may be 2-substituted aziridines. They may be 1,2-disubstituted aziridines. They may be 3-unsubstituted aziridines. They may be 3-substituted aziridines. They may be 1,2,3-trisubstituted aziridines. They may be optically active. They may be chiral. They may be achiral. They may be racemic. Aziridine Group Transfer via Transient N-Aziridinyl Radicals Aziridines are the smallest nitrogen-containing heterocycles. Strain-enhanced electrophilicity renders aziridines useful synthetic intermediates and gives rise to biological activity. Classical aziridine syntheses — based on either [2+1] cycloadditions or intramolecular substitution chemistry — assemble aziridines from acyclic precursors. In this present invention, N-aziridinyl radicals were introduced as a reactive intermediate that enables transfer of intact aziridine fragments in organic synthesis. Transient N-aziridinyl radicals are generated by reductive activation of N-pyridinium aziridines and are directly characterized by spin-trapped EPR spectroscopy. In the presence of O2, N-aziridinyl radicals add to styrenyl olefins to afford 1,2- hydroxyaziridination products. These results establish aziridinyl radicals as new reactive intermediates in synthetic chemistry and demonstrate aziridine group transfer as a viable synthetic disconnection. Aziridines are important synthetic building blocks and represent electrophilic pharmacophores in a variety of organic small molecule therapeutics and natural products (FIG. 42A) [26, 27]. Aziridines are typically constructed via [2+1] cycloadditions between either olefins with nitrene equivalents or imines with carbene equivalents, or via intramolecular nucleophilic substitution chemistry within pre-functionalized substrates (FIG.42B) [28-32]. N-Alkylation and metal-catalyzed C–N cross-coupling reactions between N–H aziridines and appropriate electrophiles provide opportunities to functionalize the exocyclic N–H valence of pre-formed aziridines [33, 34], however, aziridine ring-opening chemistry to deliver 1,2- aminofunctionalization products is often observed during these transformations [35-37]. Methods to transfer intact aziridines to relatively unfunctionalized substrates, such as aziridine transfer to C–H bonds or aziridine addition to olefinic substrates, would be powerfully enabling synthetic disconnections, but are currently unavailable. FIG.42A shows selected aziridine-containing natural products. FIG.42B shows classical synthetic disconnections for aziridines and N-functionalization chemistry. FIG. 42C shows one embodiment of the present invention, the synthesis and reactivity of N-aziridinyl radicals, which engage in intermolecular olefin addition chemistry. PC = photocatalyst. Developing aziridine transfer chemistry as a method to install this motif into widely available starting materials was attractive. Transfer of intact aziridine fragments to olefinic substrates, for example via 1,2-aziridine functionalization processes, would complement extant olefin aziridination reactions via nitrene transfer and provide a new disconnection in aziridination chemistry. Based on the burgeoning literature of N-centered radical addition to olefins [38-52], it was envisioned that facile access to N-aziridinyl radicals would enable aziridine transfer chemistry to be realized. Given the strength of aziridine N–H bonds (~92 kcal / mol) [53, 54] in comparison to the C–N bonds of the strained three-membered ring (~54 kcal / mol)

[0055] , direct generation of N- aziridinyl radicals from N–H precursors was viewed as unlikely, especially under the mild conditions needed for broad substrate compatibility. Much of the progress in N-centered radical chemistry has resulted from the availability of predictable methods to generate radicals via single- electron transfer (SET) between R2N–X (LG = –Cl, –Br, –O2CR) reagents and either transition metal catalysts [56-62] or photocatalysts [63, 64]. As such, it was speculated that an N-substituted aziridine featuring a (photo)cleavable N-substituent could provide selective entry to aziridine radical chemistry. N-pyridinium aziridines as electrophiles in C–N cross coupling chemistry was previously developed

[0065] . The present invention contemplated that N-aziridinyl radicals would be generated from these isolable precursors if mild conditions were developed for the selective activation of the N–N bond [66-73]. In the present invention, it is demonstrated that the reductive photoactivation of N-pyridinium aziridines generates N-aziridinyl radicals that are characterized by spin-trapped EPR spectroscopy. DFT studies indicate the N-aziridinyl radical is planar with the unpaired spin in a p-orbital, which was hypothesized results in electrophilic reactivity

[0074] . In the synthetic context, the transient N-aziridinyl radicals can be trapped with olefinic substrates in the presence of O2to access products of 1,2-hydroxyaziridination (FIG.42C). Together, these results establish N-aziridinyl radicals a new reactive intermediate for synthetic chemistry and demonstrate aziridine group-transfer as a viable synthetic disconnection. The development of aziridine transfer chemistry was initiated with N-pyridinium aziridine 102a (tpp = triphenylpyridinium), which displays a reductive electrochemical feature at –0.85 V vs. Fc+ / Fc

[0075] . It was hypothesized that in the presence of an appropriate photocatalyst, reductive quenching would unveil an N-aziridinyl radical. Consistent with this, photolysis of a MeCN solution of 102a in the presence of Ir(ppy)3(Ir(III)* / Ir(IV) = –1.73 V vs. Fc+ / Fc)

[0076] , triethyl amine, and radical accepter 101, afforded 103, the product of aziridine transfer (Eqn.1). (1) FIG.43 shows cconditions: 102 (0.1 mmol), 104 (0.15 mmol), Et3N (0.2 mmol), Ir(ppy)3(1.0 mol%), LiBr (0.1 mmol), blue LED irradiation at 23 ºC in MeCN:H2O (1:1, 2.0 mL).b0.2 mL CH2Cl2was added as the olefin 104n is sparingly soluble in MeCN. Isolated yields. With conditions in hand to promote N-aziridinyl radical transfer, the present invention sought to engage this novel fragment in addition chemistry to olefins. To this end, photolysis (blue LED) of 102a, styrene, Ir(ppy)3(1.0 mol%), and Et3N in an O2-saturated H2O:MeCN solution resulted in compound 105a, the product of olefin 1,2-hydroxyaziridination, in 35% yield (1:1 dr, Table 3, entry 1). Addition of LiBr, which presumably serves as a Lewis acid, increased the yield of hydroxyazirdine 105a to 42% (50 mol% LiBr, entry 2) and 69% (1.0 equiv LiBr, entry 3). No aziridine transfer products were obtained in the absence of Et3N, photocatalyst, or light (entries 4- 6). Changes to the relative stoichiometry of olefin 104a and aziridine radical precursor 102a did not improve the efficiency of olefin hydroxyaziridination (entries 7 and 8). Using unsubstituted N- pyridinium aziridine 102a’ afforded only 29% yield of 105a, which is consistent with the more negative reduction potential of unsubstituted pyridinium aziridines as compared to 2,4,6-triphenyl pyridinium aziridines

[0075] . In the absence of water, the reaction afforded 62% 105a but was less clean which complicated purification, and thus the optimized conditions utilized 1:1 H2O:MeCN mixture (see Example 16 for optimization details). Compound 105a can be envisioned as the product of epoxide opening with an aziridine nucleophile, which to our knowledge is an unknown transformation. After identifying conditions of N-aziridinyl radical transfer, the present invention sought to use radical precursor 102a to canvass the reactivity of this fragment in the aziridine transfer protocol. Substrates with electron-donating group such as 4-Me– (104b) and 4-OMe– (104c) substituents afforded 105b and 105c in 58 and 49% yield, respectively. Para-chlorinated (104d) and -fluorinated (104e) substrates engage in efficient hydroxyaziridination, and ortho-brominated 104f affords the corresponding hydroxyaziridine in 56% yield, which evidences the compatibility of the protocol with large ortho substituents. Electron-deficient substrates, such as 104g (–CF3), 104h (–CN), and 104i (–CO2Et) are hydroxyaziridinated to 105g, 105h, and 105i in 56-64% yield; 3-nitrostyrene furnished the corresponding aziridine-addition product 105j in 81% isolated yield. Heterocycle-containing substrates are also compatible with the reaction conditions, with 2-vinyl pyridine delivering product 105k in 40% yield. 1,1-Disubstituted styrenes were competent substrates: α-methyl- and phenyl-substituted styrene (104l and 104m) gave the hydroxylated products (105l and 105m) with moderate yields (41 and 44%, respectively); 1,2-disubstituted derivatives were not productive coupling partners. Finally, styrenes derived from drug molecules such as indomethacin and ibuprofen also provided the desired products (105n and 105o) in 48 and 54% yield, respectively. Consistent with the high N–H BDE and proclivity of aminyl radicals to engage in H-atom abstraction reactions, N–H aziridines were often observed as byproducts of the developed aziridine transfer chemistry

[0077] . Diverse N-aziridinyl radical precursors (102) are also accommodated in the hydroxyaziridination protocol. Electron-neutral (105p-105r) and electron-deficient (105s-105v) N-aziridinyl radical precursors delivered addition products in modest to good yields. N-pyridinium aziridines with electron-donating substituents, such as radical precursors 102i and 102j were less efficient, delivering hydoxyaziridines 105w and 105x in 42 and 46% yield, respectively. The less efficient coupling of electron-rich precursors is consistent with more challenging one-electron reduction of these substrates. Photoactivation of naphthyl styrene-derived N-pyridinium aziridine salt 102k in the presence of 3-nitrostyrene delivered product 105y in 69% isolated yield. Aziridine 102l, derived from 2-vinyl benzothiophene is also compatible with the aziridine-transfer protocol, delivering 105z with 57% yield. Moreover, N-pyridinium aziridines derived from pharmaceutical scaffolds such as indomethacin (102m), tufnil (102n), ibuprofen (102o), and probenecid (102p) all engage is efficient aziridine transfer chemistry (52-65% yields). Table 3: Optimized conditions: 104a (0.15 mmol), 2a (0.10 mmol), Ir(ppy)3(1.0 mol%), Et3N (0.2 mmol), LiBr (0.10 mmol) in MeCN:H2O (1:1, 2.0 mL) under blue LED irradiation.aYields were determined by1H NMR against 1,3,5-trimethoxybenzene. ) FIG.44A shows Conditions: 106 (0.1 mmol), 104 (0.15 mmol), Et3N (0.2 mmol), Ir(ppy)3(1.0 mol%), LiBr (0.1 mmol), blue LED irradiation at 23 ºC in MeCN:H2O (1:1, 2.0 mL).b0.2 mL CH2Cl2was added as the olefin 104p was sparingly soluble in MeCN. Isolated yields. FIG.44B shows an unsubstituted aziridine was engaged into photocatalytic reaction to get hydroxyazirinated product 109 involving simplest aziridinyl radical. A shows Conditions: 106 (0.1 mmol), 104 (0.15 mmol), Et3N (0.2 mmol), Ir(ppy)3(1.0 mol%), LiBr (0.1 mmol), blue LED irradiation at 23 ºC in MeCN:H2O (1:1, 2.0 mL).b0.2 mL CH2Cl2was added as the olefin 104p was sparingly soluble in MeCN. Isolated yields. B shows unsubstituted aziridine was engaged into photocatalytic reaction to get hydroxyazirinated product 109 involving simplest aziridinyl radical. Consistent with the observations noted above for electron rich N-aziridinyl radical precursors, photoactivation of N-pyridinium aziridines derived from aliphatic olefins is less efficient than those derived from styrenes. Photoactivation of cyclohexene-derived N-pyridinium aziridine 106 in the presence of styrene (104a) afforded hydroxyaziridinated product 107a in 42% yield. A small family of different substituted styrene derivatives were treated with 106 under blue- light irradation and all afforded the corresponding aziridine-transfer products (107b-107d, 33-48% isolated yield). Complex styrene derivatives, such as indomethacin derived 104p, could be engaged similarly, albeit in low yield: Product 107e was isolated in 18% yield. Finally, access to ethylene-derived N-pyridinium aziridine 108 provided the opportunity to evaluate the transfer of the simplest, completely unsubstituted N-aziridinyl radical (FIG.44B).1,2-Hydroxyaziridination of styrene with an unsubstituted aziridine radical affords 2-hydroxy-2-phenyl-1-aziridinoethane (109, HPAE), which is currently being used as an experimental anticancer agent against neuroblastoma

[0078] , in 22% yield. The development of hydroxyaziridination chemistry was predicated on the hypothesis that reductive activation of N-pyridinium aziridines would afford transient N-aziridinyl radicals. DFT optimization of the parent N-aziridinyl radical indicates a planar geometry with the unpaired spin in a p-orbital, which may give rise to the observed electrophilic reactivity (A)

[0074] . Consistent with the addition of an N-aziridinyl radical to the olefinic partner, aminohydroxylation of radical clock

[0079] 104q afforded a mixture of hydroxyaziridination and cyclopropyl ring opening products (i.e., 110, B). Further, the addition of TEMPO to the hydroxyaziridination of 102a led to complete inhibition of the olefin functionalization chemistry. Together, these observations are consistent with the intermediacy of bona fide N-aziridinyl radical intermediates. To more directly evaluate the intermediacy of N-aziridinyl radicals, the photolysis of a MeCN solution of 102a, Ir(ppy)3, and Et3N in the presence of N-tert-butyl-a-phenylnitrone (PBN) was carried out. PBN is an attractive spin trap because unlike BHT or TEMPO, radical intermediates form kinetically persistent covalent adducts with PBN that can be characterized by a combination of electron paramagnetic resonance (EPR) spectroscopy and mass spectrometry. The EPR spectrum following photolysis of a mixture of 102a and PBN under the conditions described above (i.e., Ir(ppy)3(1.0 mol%), Et3N, green LED) displayed a triplet of quartets attributed to PBN-trapped aziridnyl radical with aN(PBN)= 14.0 G, aH= 1.8 G, and aN(aziridinyl)= 2.1 G (C). The apparent triplet of quartet is due to the unresolved / overlapped hyperfine couplings from aHand aN(aziridinyl). Formation of PBN-trapped aziridinyl radical was further confirmed by mass analysis of the EPR sample where HRMS-ESI: calculated for [M+H]+= 295.1805, observed [M+H]+= 295.1797. Stern-Volmer quenching studies as a function of both [102a] and [Et3N] indicate that 102a is the primary quencher for this reaction (Example 17 Section D.5). As the hydroxyaziridination reaction is carried out under O2, one might envision that reductive quenching could also be accomplished by O2. To evaluate this possibility, cyclic voltammograms (CVs) of 102a were collected. Under N2, compound 102a displays an irreversible reductive event at –0.85 V vs Fc+ / Fc; under an aerobic atmosphere, in addition to the reductive wave at –0.85 V, an O2reduction wave is observed at –1.2 V vs Fc+ / Fc. From these data, 102a appears to be a more competent electron transfer partner than O2, although given the high concentration of O2during olefin functionalization, O2-mediated reduction of 102a may contribute to the overall observed catalytic rates (Example 14). The available data is consistent with the mechanism illustrated in FIG.46. Single-electron transfer from the Ir(III) catalyst to 102a can generate aziridinyl radical I which is trapped by the styrene to generate benzylic radical II

[0080] . Reaction of II with O2ultimately gives rise to hydroxyaziridination product 105a. FIG. 46 shows potential photocatalytic mechanism for N- aziridinyl radical generation and transfer. In summary, N-aziridinyl radicals are a novel reactive intermediate that enables transfer of intact aziridines to olefinic substrates. N-aziridinyl radicals are generated under mild photochemical conditions, which enables the strained fragment to engage in intermolecular addition chemistry without appreciable ring opening. Olefin 1,2-hydroxyaziridination was demonstrated with a variety of aziridine precursors, including the simplest unsubstituted fragment. Radical trapping experiments supported the formation and intermediacy of freely diffusing N- aziridinyl radical intermediates. Together, these results provide new disconnections for aziridines in functional organic molecules and demonstrate the accessibility of strained aminyl radical intermediates in synthesis. EXAMPLES The following examples are provided in order to demonstrate and further illustrate certain preferred embodiments and aspects of the present invention and are not to be construed as limiting the scope thereof. EXAMPLE 1 A.1 Materials All chemicals and solvents were obtained as ACS reagent grade and used as received. Hydroxylamine-O-sulfonic acid, dehydroepiandrosterone, and 4- ethoxylcarbonylphenylboronic acid (11c) were purchased from Matrix. Pyridine, potassium carbonate, methyl tert-butyl ether, and vinylcyclohexane (2l) were purchased from BTC. Potassium phosphate, trifluoroacetic acid, cyclohexene (2a), 1-octene (2g), allylbenzene (2n), but-3-en-1-ylbenzene (2o), iodomethane, ethylene (2aa), propylene (2ab), 1,3,5- trimethoxybenzene, and triethyl benzene-1,3,5-tricarboxylate were purchased from Sigma Aldrich. Trifluoromethanesulfonic aicd, mesitylsulfonyl chloride, tert-butyl-N- hydroxycarbamate, 4-bromo-1-butene, 6-bromo-1-hexene, ibuprofen, celecoxib, oxaprozin, benzoic acid, 6-chloro-1-hexene (2h), di-tert-butyl decarbonate, and isobutylene (2ac) were purchased from Oakwood. Geraniol, cyclooctene (2c), and norbornene (2e) were purchased from Alfa Aesar. Cyclopentene (2b), (+)-δ3-carene (2d), and cis-cyclooctadiene (2f) were purchased from TCI. tert-Butyl 4-methylenepiperidine-1-carboxylate (2q), β-caryophyllene (2x), (R)- carvone (2z), and 3,5-bis(trifluoromethyl)benzeneboronic acid (11a) were purchased fromAmbeed. 1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) was refluxed for 12 h under N2 over 3 Àmolecular sieves, distilled, and stored in a Straus flask

[0081] . Drydichloromethane andacetonitrile (purchased from Fisher scientific, HPLC grade) were obtained from a dryingcolumn and stored over activated 4 À molecular sieves

[0082] . NMR solvents were purchasedfrom Cambridge Isotope Laboratories and were used as received. All reactions were carried out under an ambient atmosphere unless otherwise noted. Hex-5-en-1-yl benzoate (2i)

[0083] , 6-azidohex-1-ene (2k)

[0084] , pent-4-en-1-ylbenzene (2p)

[0085] , 1-(but- 3-en-1-yl)-4-vinylbenzene (2r)

[0086] , (E)-3,7-dimethylocta-2,6-dien-1-yl acetate (2v)

[0087] , (E)-2- (3,7-dimethylocta-2,6-dien-1-yl)-3a,7a-dihydro-1H-isoindole-1,3(2H)-dione (2w)

[0087] , tert- Butyl ((4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)phenyl)sulfonyl)carbamate (S4)

[0088] , (4-bromophenyl)-λ3-iodanediyl diacetate (S5a)

[0089] , (4-cyanophenyl)-λ3-iodanediyl diacetate (S5b)

[0089] , (4-nitrophenyl)-λ3-iodanediyl diacetate (S5c)

[0089] , and iodosyl-4- methylbenzene (S6d)

[0090] were synthesized according to literature methods. was prepared from celecoxib according to a literature procedure. Iodosyl-4-methoxybenzene (S6e) was synthesized according to a reported procedure

[0090] from (4-methoxyphenyl)-λ3-iodanediyl diacetate, which was prepared via a literature method

[0091] . A.2 Characterization Details1H and13C NMR spectra were recorded on an Inova 500 FT NMR (Varian), an AcsendTM400 NMR (Bruker), or an AcsendTM400 NMR (Bruker) and werereferenced against residual proteo solvent signals: CDCl3(7.26 ppm, 1H; 77.16 ppm, 13C),CD3OD (3.31 ppm,1H; 49.00 ppm,13C), (CD3)2SO (2.50 ppm,1H), and acetonitrile-d3(1.94 ppm,1H; 1.32 ppm,13C)

[0092] .1H NMR data are reported as follows: chemical shift (δ, ppm), (multiplicity: s (singlet), d (doublet), t (triplet), m (multiplet), br (broad), integration).13C NMR data are reported as follows: chemical shift (δ, ppm). Mass spectrometry data were recorded on either Orbitrap FusionTMTribridTMMass Spectrometer or Q ExactiveTMFocus Hybrid Quadrupole-OrbitrapTMMass Spectrometer from ThermoFisher Scientific. For single-crystal X-ray diffraction analysis of t-5f, 5z, 12c, and 12f, a Bruker APEX 2 Duo X- ray (three-circle) diffractometer was used for crystal screening, unit cell determination, and datacollection. A crystal suitable for X-ray diffraction was mounted on a MiTeGen dual-thicknessmicro-mount and placed under a cold N2stream (Oxford). The X-ray radiation employed wasgenerated from a Mo sealed X-ray tube (Kα= 0.70173 Å with a potential of 40kV and a current of40 mA). Bruker AXS APEX II software was used for data collection and reduction. Absorption corrections were applied using SADABS. A solution was obtained using XT / XS in APEX2 and refined in Olex2 [93-95]. Hydrogen atoms were placed in idealized positions and were set riding on the respective parent atoms. All non-hydrogen atoms were refined with anisotropic thermal parameters. The structure was refined (weighted least squares refinement on F2) to convergence

[0095] . B. Synthesis and Characterization EXAMPLE 2 B.1 Synthesis of N-Aminopyridinium Salts Synthesis of N-aminopyridinium triflate (3) N- ofliterature methods.16A 250-mL round-bottom flask was charged with a freshly preparedsolutionof hydroxylamine-O-sulfonic acid (11.3 g, 100. mmol, 1.00 equiv.) in H2O (64 mL).Pyridine(24.0 mL, 300. mmol, 1.00 equiv.) was added. The reaction was heated at 90 ℃ for 20 min before being cooled to 23 ℃. With vigorous stirring, potassium carbonate (13.8 g, 100. mmol, 1.00 equiv.) was added to the reaction vessel, and the mixture was stirred for 5 min. Volatiles were removed under reduced pressure and 120 mL of ethanol was added. Solids were removed by filtration. The filtrate was cooled to 0 ℃ and TfOH (15.0 g, 8.80 mL, 100. mmol, 1.00 equiv.) was added dropwise. The solution was concentrated under reduced pressure until about 20 mL was left in the flask. The concentrated solution was cooled to – 20 ℃ to induce crystallization. The precipitate was filtered and dried under vacuum to give the title compound 3 as an off-white solid (16.5 g, 67% yield).1H NMR (400 MHz, CD3CN) δ 8.57 (d, J = 6.2 Hz, 2H), 8.28 (t, J = 7.7 Hz, 1H), 7.92 (t, J = 7.3 Hz, 2H), 7.11 (s, 2H).19F NMR (377 MHz, CD3CN) δ –79.1. These spectral data are well-matched to those reported in the literature

[0096] . EXAMPLE 3 Synthesis of O-(mesitylsulfonyl)hydroxylamine (S2) tert- following modification of literature methods

[0097] . A 100-mL round-bottom flask charged with mesitylenesulfonyl chloride (2.19 g, 10.0 mmol, 1.00 equiv.), tert-butyl-N-hydroxycarbamate (1.33g, 10.0 mmol, 1.00 equiv.), and methyl tert-butyl ether (MTBE, 25 mL). The mixturewas spargedwith N2and cooled to 0 ℃. Triethylamine (1.39 mL, 10.0 mmol, 1.00 equiv.) wasadded dropwisewith stirring after which the reaction was stirred for 2 h (Reaction progress was monitored by thin- layer chromatography (TLC) using a 7 : 3 hexanes : ethyl acetate mobile phase). The mixture was filtered, the obtained solids were washed with MTBE, and the filtrate was concentrated under reduced pressure. Hexanes were then added, and the resulting precipitate was collected by filtration.The obtained solid was dried under vacuum at 23 ℃ to affordcompound S1 as a white solid (2.70g, 86%). 1H NMR (400 MHz, CDCl3) δ 7.51 (s, 1H), 6.99(s, 2H), 2.68 (s, 6H), 2.32 (s, 3H), 1.32(s, 9H). These spectral data are well-matched to those reported in the literature

[0097] . A 100-mL round-bottom flask was charged with trifluoroacetic acid (7.9 mL, 0.10 mol, 12 equiv.), and was cooled to 0 ℃. tert-Butyl ((mesitylsulfonyl)oxy)carbamate (S1, 2.70 g, 8.57 mmol, 1.00 equiv.) was added to the reaction vessel in 3 portions over 20 min. The reaction was stirred at 0 ℃ for 90 min (Reaction progress was monitored by thin-layer chromatography (TLC) using an 8:2 hexanes : ethyl acetate mobile phase.). Crushed ice was added followed by water (15 mL). After 15 min, the obtained precipitate was collected by filtration, washed with water until the pH of the wash measured 7 by litmus, and dried to afford MSH (S2) as a white solid (3.14 g, 146%) (Caution is needed for handling MSH. MSH has been reported to be unstable and potentially explosive when dry. The >100% apparent yield is due to the water content of the wet MSH.) and stored below 0 ℃.This was used without further drying or purification.1H NMR (400MHz, DMSO-d6) δ 6.75 (s,2H), 2.49 (s, 6H), 2.17 (s, 3H). These spectral data are well-matchedto those reported in the literature

[0097] . EXAMPLE 4 Synthesis of N-aminopyridinium 2,4,6-trimethylbenzenesulfonates (S3) N-Aminopyridinium prepared according to the following modification of literature methods

[0098] . A 20-mL scintillation vial was charged withMSH (S2, 0.60 mmol, 1.0 equiv.) and CH2Cl2(4.0 mL). The appropriate pyridine derivative(0.60mmol, 1.0 equiv.) was added. The mixture was stirred for 30 min at 23 ℃ and concentratedunder reduced pressure. The desired N-aminopyridinium salts (S3) werepurified bycrystallization from MeOH / Et2O. Characterization data are collected below, for compoundstructures seeFIG. 35.1-Aminopyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3a). Prepared from pyridine (0.600 mmol), and obtained as a white solid (34.6 mg, 20%).1H NMR (400 MHz, DMSO) δ 8.77 (d, J = 6.2 Hz, 2H), 8.47 (s, 2H), 8.27 (t, J = 7.9 Hz, 1H), 8.01 (t, J = 7.1 Hz, 2H), 6.74 (s, 2H), 2.49 (s, 6H), 2.17 (s, 3H). These spectral data are well-matched to those reported in the literature

[0099] . 1-Amino-4-methoxypyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3b). Prepared from 4-methoxypyridine (0.400 mmol), and obtained as a white solid (65.0 mg, 50%).1H NMR (500MHz,CDCl3) δ 8.86 (d, J = 7.6 Hz, 2H), 8.14 (s, 2H), 7.06 (d, J = 7.6 Hz, 2H), 6.80 (s, 2H), 3.95(s, 3H),2.61 (s, 6H), 2.22 (s, 3H). These spectral data are well-matched to those reported in the literature

[0100] . 1-Amino-4-methylpyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3c). Prepared from 4- methylpyridine (0.600 mmol), and obtained as an off-white solid (67.5 mg, 36%).1H NMR (400 MHz, DMSO) δ 8.64 (d, J = 6.8 Hz, 2H), 8.22 (s, 2H), 7.83 (d, J = 6.5 Hz, 2H), 6.74 (s, 2H), 2.52 (s, 3H), 2.49 (s, 6H), 2.17 (s, 3H). These spectral data are well-matched to those reported in the literature

[0099] . 1-Amino-4-(tert-butyl)pyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3d). Prepared from 4- (tert-butyl)pyridine (0.600 mmol), and obtained as a colorless oil (130 mg, 62%).1H NMR (400 MHz, DMSO) δ 8.68 (d, J = 7.1 Hz, 2H), 8.28 (s, 2H), 8.02 (d, J = 7.1 Hz, 2H), 6.74 (s, 2H), 2.49(s, 6H), 2.17 (s, 3H), 1.33 (s, 9H).13C NMR (101 MHz, DMSO) δ 164.1, 142.8, 138.2, 136.2,135.9,129.8, 125.0, 35.7, 29.6, 22.7, 20.3. HRMS-ESI+ (m / z): [M]+ calcd. for C9H15N2+,151.1230; found,151.1227. 1-Amino-4-phenylpyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3e). Prepared from 4- phenylpyridine (0.600 mmol), and obtained as a yellow solid (128 mg, 58%).1H NMR (400 MHz, DMSO) δ 8.81 (d, J = 7.1 Hz, 2H), 8.48 (s, 2H), 8.36 (d, J = 7.1 Hz, 2H), 8.07–7.85 (m, 2H), 7.69– 7.33 (m, 3H), 6.74 (s, 2H), 2.51 (s, 6H), 2.15 (s, 3H).13C NMR (101 MHz, DMSO) δ 149.4, 142.6,138.5, 136.4, 135.9, 133.7, 131.3, 129.9, 129.6, 127.6, 124.6, 22.7, 20.3. HRMS-ESI+ (m / z):[M]+calcd. for C11H11N2+, 171.0917; found, 171.0914. 1-Amino-4-chloropyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3f). Prepared from 4- chloropyridine hydrochloric acidd(0.600 mmol), and obtained as a yellow solid (29.7 mg, 15%).1H NMR (400 MHz, DMSO) δ 8.76 (d, J = 7.3 Hz, 2H), 8.52 (s, 2H), 8.17 (d, J = 7.2 Hz, 2H), 6.74 (s, 2H), 2.49 (s, 6H), 2.17 (s, 3H). These spectral data are well-matched to those reported in the literature

[0099] . 1-Amino-4-(trifluoromethyl)pyridin-1-ium 2,4,6-trimethylbenzenesulfonate (S3g). Prepared from 4-(trifluoromethyl)pyridine (0.600 mmol) and obtained as a white solid (131 mg, 60%).1H NMR (500 MHz, DMSO) δ 8.88 (s, 2H), 8.69 (d, J = 6.5 Hz, 2H), 8.14 (d, J = 6.7 Hz, 2H), 6.48 (s, 2H), 2.23 (s, 6H), 1.90 (s, 3H).19F NMR (377 MHz, DMSO) δ –63.3.13C NMR (126 MHz, DMSO)δ 142.5, 138.0, 136.4, 136.1 (q, J = 35.5 Hz), 135.9, 129.9, 124.9 (q, J = 3.7 Hz), 121.6(q, J =273.8 Hz), 22.7, 20.3. HRMS-ESI+ (m / z): [M]+ calcd. for C6H6F3N2+, 163.0478; found,163.0474.EXAMPLE 5 B.2 Preparation of Aliphatic Olefins General A 20-mL scintillation vial was charged with the appropriate carboxylic acid (1.50 mmol, 1.00 equiv.), K2CO3(311 mg, 2.25 mmol, 1.50 equiv.), and DMF (10.0 mL). The appropriate bromoolefin (1.65 mmol, 1.10 equiv.) was added and the reaction was stirred at 60 ℃ for 12 h. Thereaction mixture was cooled to 23 ℃ and water (15 mL) was added. The mixture wasextractedwith EtOAc (3 X 10 mL). The combined organic layers were washed with H2O (4 X 10 mL),washed with brine (30 mL), dried over Na2SO4, and concentrated under reducedpressure. Thecrude mixture was purified by silica gel flash chromatography to afford the corresponding aliphatic olefin (2). For structures see FIG.36.But-3-en-1-yl benzoate (2m). Prepared via the general procedure from benzoic acid (800 mg,6.55mmol), and obtained as a colorless oil (1.13 g, 98%). 1H NMR (400 MHz, CDCl3) δ 8.04(d, J =7.0 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 5.88 (ddt, J = 17.0, 10.2, 6.7 Hz, 1H), 5.30 – 4.95 (m, 2H), 4.38 (t, J = 6.7 Hz, 2H), 2.53 (qt, J = 6.7, 1.4 Hz, 2H). These spectral data are well-matched to those reported in the literature

[0101] . Hex-5-en-1-yl 2-(4-isobutylphenyl)propanoate (2s). Prepared via the general procedure fromibuprofen (1.00 g, 4.85 mmol), and obtained as a colorless oil (1.30 g, 93%).1H NMR (400MHz,CDCl3) δ 7.20 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 8.1 Hz, 2H), 5.74 (ddt, J = 16.9, 10.2, 6.7 Hz,1H),5.12–4.73 (m, 2H), 4.06 (t, J = 6.6 Hz, 2H), 3.68 (q, J = 7.2 Hz, 1H), 2.44 (d, J = 7.2 Hz, 2H), 2.08– 1.95 (m, 2H), 1.84 (dp, J = 13.6, 6.8 Hz, 1H), 1.59 (dq, J = 8.6, 6.6 Hz, 2H), 1.49 (d, J = 7.2 Hz, 3H), 1.35 (tt, J = 9.8, 6.4 Hz, 2H), 0.90 (d, J = 6.6 Hz, 6H). These spectral data are well- matched to those reported in the literature

[0083] . Hex-5-en-1-yl 3-(4,5-diphenyloxazol-2-yl)propanoate (2t). Prepared via the general procedurefrom oxaprozin (587 mg, 2.00 mmol), and obtained as a colorless oil (727 mg,97%). 1H NMR(400 MHz, CDCl3) δ 7.60 (ddd, J = 23.9, 8.2, 1.6 Hz, 4H), 7.41–7.27 (m, 6H),5.76 (ddt, J = 16.9,10.2, 6.7 Hz, 1H), 5.14–4.83 (m, 2H), 4.13 (t, J = 6.6 Hz, 2H), 3.19 (t, J = 7.5 Hz, 2H), 2.91 (t, J = 7.5 Hz, 2H), 2.11–2.00 (m, 2H), 1.72–1.59 (m, 2H), 1.45 (tt, J = 10.1, 6.3 Hz, 2H). These spectral data are well-matched to those reported in the literature

[0102] . tert-Butyl but-3-en-1-yl((4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)phenyl)sulfonyl)carbamate (2u). Prepared via the general procedure from N-Boc-celecoxib S4 (1.50 mmol)andobtained as a white solid (743 mg, 92%). 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.8 Hz,2H),7.46 (d, J = 8.8 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 7.10 (d, J = 8.2 Hz, 2H), 6.74 (s, 1H), 5.79 (ddt,J = 17.1, 10.2, 7.0 Hz, 1H), 5.32–4.96 (m, 2H), 3.96–3.79 (m, 2H), 2.48 (q, J = 7.2 Hz, 2H),2.38(s, 3H), 1.36 (s, 9H). 19F NMR (377 MHz, CDCl3) δ –62.5. 13C NMR (126 MHz, CDCl3) δ150.8,145.4, 144.3 (q, J = 38.6 Hz), 143.0, 139.9, 139.7, 134.3, 129.9, 129.1, 128.9, 125.9, 125.0,121.2 (q, J = 269.2 Hz), 117.8, 106.6, 84.7, 46.7, 34.7, 28.0, 21.4. HRMS-ESI+(m / z):[M+1]+calcd. for C26H29F3N3O4S+, 536.1825; found, 536.1817. Hept-6-enenitrile (2j). To NaCN (150 mg, 3.06 mmol, 1.02 equiv.) in a 50-mL round bottom flask was added DMSO (10.0 mL), followed by 6-bromohex-1-ene (489 mg, 3.00 mmol, 1.00 equiv.). The mixture was stirred for 12 h, after which TLC monitoring indicated completion of the reaction(100% hexanes, visualized by permanganate stain). Dilute aqueous NaOH (10mL) was added. Themixture was extracted with CH2Cl2(3 X 10 mL). The combined organic layers were washed withH2O (4 X 10 mL), followed by brine (20 mL), dried over Na2SO4andconcentrated under reducedpressure. The crude mixture was filtered through a silica plugto afford the title compound as acolorless oil (270 mg, 82%). 1H NMR (400 MHz, CDCl3) δ5.77 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H),5.06–5.01 (m, 1H), 5.01–4.97 (m, 1H), 2.35 (t, J = 7.0 Hz, 2H), 2.17–2.02 (m, 2H), 1.73–1.61 (m, 2H), 1.60–1.50 (m, 2H). These spectral data are well- matched to those reported in the literature

[0103] . O-Methyl dehydroepiandrosterone (2y)

[0104] . In an N2-filled glovebox, NaH dispersed in mineral oil was washed with pentane and dried. A 200-mL Schlenk flask was charged withdehydroepiandrosterone (2.32 g, 8.04 mmol, 1.00 equiv.), and anhydrous THF (50 mL). NaH(220mg, 9.16 mmol, 1.14 equiv.) was added and the resulting mixture was stirred under N2 at 23 ℃ for30 min to afford an orange-colored mixture. The reaction vessel was removed from the glovebox. Iodomethane (5.69 g, 2.50 mL, 40.1 mmol, 5.00 equiv.) was added dropwise and the resulting mixture was heated to 40 ℃ and stirred for 2.5 h. The reaction was cooled to 23 ℃, water (150mL) was added, and the mixture was extracted with EtOAc(3 X 50 mL). The combined organiclayer was washed with brine, dried over Na2SO4, andconcentrated under reduced pressure. Thecrude mixture was purified by silica gel flash chromatography using EtOAc : hexanes (1 : 10) asthe eluent to afford the title compound asa white solid (3.58 g, 45% yield). 1H NMR (500 MHz,CDCl3) δ 5.39 (d, J = 5.4 Hz, 1H), 3.36 (s,3H), 3.07 (tt, J = 11.3, 4.5 Hz, 1H), 2.54–2.32 (m, 2H),2.23–2.02 (m, 3H), 2.01–1.79 (m, 4H), 1.73–1.60 (m, 3H), 1.61–1.37 (m, 3H), 1.34–1.23 (m, 2H), 1.11–0.96 (m, 5H), 0.89 (s, 3H). These spectral data are well-matched to those reported in the literature

[0105] . EXAMPLE 6 B.3 Aziridination of Aliphatic Olefins Some example compounds are found in FIG.37. Procedure A A 25-mL Schlenk tube was charged with N-aminopyridinium triflate (3, 0.300 mmol, 73.2 mg, 1.00equiv.), the appropriate olefin (2, 0.300 mmol, 1.00 equiv.), and 4 Å molecular sieves.Dry HFIP(1.0 mL) was added under N2and the mixture was cooled to 0 ℃. A 20-mLscintillation vialwas charged with iodosylbenzene (4, 0.600 mmol, 132 mg, 2.00 equiv.) andHFIP (2.0 mL) underN2. The HFIP solution of iodosylbenzene was then added dropwise tothe Schlenk tube at 0 ℃.The resulting mixture was allowed to warm to 23 ℃ and stirred for12 h. The reaction was filtered,the obtained solids washed with CH2Cl2(3 X 1.0 mL), and thecombined filtrate was concentratedunder reduced pressure. The crude was purified by silicagel flash chromatography, using EtOAc,CH2Cl2, 3% (v / v) MeOH / CH2Cl2, then 5% (v / v) MeOH / CH2Cl2as the eluent to afford the title compound. Procedure B A 25-mL Schlenk tube was charged with iodosylbenzene (4, 0.600 mmol, 132 mg, 2.00equiv.), 4 Å molecular sieves, and dry CH3CN (1.0 mL) under N2and the mixture was cooledto0 ℃. A 20-mL scintillation vial was charged with N-aminopyridinium triflate (3, 0.300 mmol,73.2 mg, 1.00 equiv.), the corresponding olefin (2, 0.300 mmol, 1.00 equiv.), and dryCH3CN (2.0mL) under N2. This solution was then added dropwise to the Schlenk tube, andthe mixture wasallowed to warm to 23 ℃ and stirred for 12 h. The reaction was filtered, theobtained solidswashed with CH3CN (3 X 1.0 mL), and the combined filtrate was concentratedunder reducedpressure. The crude was purified by silica gel flash chromatography usingEtOAc, CH2Cl2, 3%(v / v) MeOH / CH2Cl2, then 5% (v / v) MeOH / CH2Cl2as the eluent to affordthe title compound. A 50-mL Schlenk flask with a rubber septum was evacuated and the head space filled with the appropriate gaseous olefin (2), supplied from an inflated balloon.A 25-mL Schlenk tube was charged with N-aminopyridinium triflate (3, 0.200 mmol, 44.8 mg,1.00equiv.), 4 Å molecular sieves, and dry HFIP (1.0 mL) under N2. The mixture was cooledto –78 ℃.At this temperature, an HFIP solution (1.0 mL) of iodosylbenzene (4, 0.400 mmol,88.0 mg, 2.00equiv.) was slowly added. The Schlenk tube was then frozen (N2(l)cooling bath)and the head spacewas evacuated. The gaseous olefin was transferred to the reaction flask (maintained at –196 ℃) via a rubber hose connection. The mixture was warmed to 23 ℃, at which temperature it was stirredfor 16 h. The reaction was filtered, the obtained solids werewashed with CH3CN (3 ^^1.0 mL), and the combined filtrate was concentrated under reduced pressure. The crude was purified by silica gel flash chromatography, using EtOAc, CH2Cl2, 3% (v / v) MeOH / CH2Cl2, then 5% (v / v) MeOH / CH2Cl2as the eluent to afford the title compound. 1-(7-Azabicyclo[4.1.0]heptan-7-yl)pyridin-1-ium trifluoromethanesulfonate (5a). The titlecompound was prepared via Procedure A in a 50-mL Schlenk flask from cyclohexene (2a,2.00mmol), was purified by crystallization from CH3CN / Et2O, and was obtained as a yellow solid (494mg, 76%). 1H NMR (400 MHz, CD3CN) δ 8.80 (d, J = 5.6 Hz, 2H), 8.29 (t, J = 7.8 Hz,1H), 7.92(t, J = 7.3 Hz, 2H), 3.39–3.27 (m, 2H), 2.25–2.17 (m, 2H), 2.07–2.03 (m, 2H), 1.45–1.28 (m, 4H). These spectral data are well-matched to those reported in the literature [2]. 1-(6-Azabicyclo[3.1.0]hexan-6-yl)pyridin-1-ium trifluoromethanesulfonate (5b). Prepared viaProcedure A from cyclopentene (2b) and obtained as a yellow powder (57.9 mg, 62%).1HNMR(400 MHz, CD3CN) δ 8.83 (d, J = 5.6 Hz, 2H), 8.29 (t, J = 7.8 Hz, 1H), 7.93 (t, J = 7.3 Hz,2H),3.75 (m, 2H), 2.34–2.29 (m, 2H), 1.88 (ddt, J = 13.6, 8.9, 1.7 Hz, 2H), 1.73 (dt, J = 13.0, 8.8Hz,1H), 1.35 (dtt, J = 13.0, 10.8, 8.2 Hz, 1H).19F NMR (377 MHz, CD3CN) δ –79.3.13C NMR (101 MHz, CD3CN) δ 143.6, 142.0, 129.3, 121.9 (q, J = 320.4 Hz), 54.7, 28.3, 21.0. HRMS-ESI+(m / z): [M]+calcd. for C10H13N2+, 161.1073; found, 161.1071. 1-(9-Azabicyclo[6.1.0]nonan-9-yl)pyridin-1-ium trifluoromethanesulfonate (c-5c). Prepared viaProcedure A from cyclooctene (2c, 0.400 mmol) and obtained as a yellow oil (102 mg,73%).1H NMR (400 MHz, CD3CN) δ 8.82 (dd, J = 6.9, 1.3 Hz, 2H), 8.34–8.26 (m, 1H), 7.98–7.86 (m,2H), 3.25–3.13 (m, 2H), 2.56–2.45 (m, 2H), 1.75–1.64 (m, 2H), 1.57–1.39 (m, 8H).19F NMR(377 MHz, CD3CN) δ –79.4.13C NMR (101 MHz, CD3CN) δ 143.7, 141.0, 129.2, 122.1 (q, J =320.8 Hz), 51.3, 26.7, 26.5, 25.8. HRMS-ESI+ (m / z): [M]+ calcd. for C13H19N2+, 203.1543;found,203.1543. 1-(3,8,8-Trimethyl-4-azatricyclo[5.1.0.03,5]octan-4-yl)pyridin-1-ium trifluoromethanesulfonate(5d). Prepared via Procedure B from 3-carene (2d, 0.200 mmol)and obtained as a yellow oil (42.2mg, 56%). 1H NMR (500 MHz, CD3CN) δ 8.67 (d, J = 5.8 Hz,2H), 8.32 (t, J = 7.8 Hz, 1H), 7.96(t, J = 7.2 Hz, 2H), 3.15 (s, 1H), 2.72–2.58 (m, 1H), 2.50 (dd, J = 16.2, 9.3 Hz, 1H), 1.73 (dt, J =16.2, 3.3 Hz, 1H), 1.54–1.47 (m, 1H), 1.06 (s, 3H), 1.04 (s,3H), 0.79 (s, 3H), 0.59 (dtd, J = 33.4,9.3, 3.2 Hz, 2H).19F NMR (377 MHz, CD3CN) δ –79.4.13C NMR (126 MHz, CD3CN) δ 143.3, 141.3, 129.3, 122.0 (q, J = 320.7 Hz), 50.8, 50.7, 27.8, 24.1, 18.9, 17.8, 17.7, 16.9, 15.3, 15.0.HRMS-ESI+ (m / z): [M]+ calcd. for C15H21N2+, 229.1699; found,229.1695.1-(3-Azatricyclo[3.2.1.02,4]octan-3-yl)pyridin-1-ium trifluoromethanesulfonate (5e). Prepared viaProcedure A from norbornene (2e) and obtained as a yellow powder (69.7 mg, 69%).1HNMR(400 MHz, CD3CN) δ 8.82 (dd, J = 7.0, 1.3 Hz, 2H), 8.27 (t, J = 7.8 Hz, 1H), 8.00–7.83 (m,2H),3.41 (s, 2H), 2.81 (s, 2H), 1.62–1.52 (m, 2H), 1.49 (dt, J = 10.4, 2.2 Hz, 1H), 1.36–1.24 (m,2H),1.09–0.95 (m, 1H). 19F NMR (376 MHz, CD3CN) δ –79.3. 13C NMR (101 MHz, CD3CN) δ143.4,142.0, 129.3, 121.9 (q, J = 320.6 Hz), 49.7, 37.3, 29.3, 25.8. HRMS-ESI+(m / z): [M]+calcd.forC12H15N2+, 187.1230; found, 187.1228. (Z)-1-(9-Azabicyclo[6.1.0]non-4-en-9-yl)pyridin-1-ium trifluoromethanesulfonate (5f). Prepared via Procedure A from cyclooctadiene (2f) and obtained as a yellow oil (72.5 mg, 69%), which isa mixture of cis- and trans- isomer (c:t = 1.4:1).1H NMR (400 MHz, CD3CN) c-5f: δ 8.82 (d, J =5.7 Hz, 2H), 8.36–8.26 (m, 1H), 7.99–7.89 (m,2H), 5.66–5.56 (m, 2H), 3.32–3.20 (m, 2H), 2.53–2.38 (m, 4H), 2.40–2.28 (m, 2H), 2.16–2.08 (m, 2H). t-5f: δ 8.67 (d, J = 6.3 Hz, 2H), 8.29 (t, J = 7.8 Hz, 1H), 7.93 (t, J = 7.2 Hz, 2H), 5.82–5.65 (m, 2H), 3.07–2.92 (m, 1H), 2.85–2.72 (m, 1H),2.53–2.21 (m, 4H), 2.09–2.06 (m, 2H),1.43–1.26 (m, 1H), 0.90–0.79 (m, 1H).19F NMR (376 MHz,CDCl3) δ –78.3.(1H of t-5f was taken from sample with enriched purity via preparative HPLC.1H of c-5f was obtained by comparison of the mixture against the purified sample. The amount of pure t-5f sample was not suitable for13C acquisition (See Figure S2).)13C NMR (101 MHz, CDCl3),mixture of c-5f and t-5f: δ 142.6, 142.2, 140.6, 139.9, 131.8, 130.7, 129.9, 129.1, 128.8,120.8 (q, J= 320.4 Hz), 54.3, 51.4, 50.8, 50.6, 28.6, 27.6, 25.1, 24.6, 23.6. HRMS-ESI+(m / z):[M]+ calcd.for C13H17N2+, 201.1386; found, 201.1386. 1-(2-Hexylaziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5g). Prepared via Procedure Afrom 1-octene (2g, 0.600 mmol) and obtained as a yellow oil (153 mg, 72%).1HNMR (400 MHz,CD3CN) δ 8.76 (d, J = 6.8 Hz, 2H), 8.32 (t, J = 7.8 Hz, 1H), 7.94 (t, J = 7.3 Hz,2H), 3.17–3.06(m, 1H), 3.03 (dd, J = 8.4, 2.6 Hz, 1H), 2.75 (dd, J = 5.7, 2.6 Hz, 1H), 1.82–1.70 (m, 1H), 1.73–1.63 (m, 1H), 1.65–1.52 (m, 2H), 1.46–1.37 (m, 1H), 1.40–1.30 (m, 4H), 0.95–0.87 (m, 3H). 19FNMR (376 MHz, CDCl3) δ –78.4.13C NMR (101 MHz, CDCl3) δ 142.7, 140.1, 128.8, 47.7, 40.6,31.7, 31.3, 29.1, 26.6, 22.6, 14.2. HRMS-ESI+ (m / z): [M]+ calcd. for C13H21N2+,205.1699; found,205.1700. 1-(2-(4-Chlorobutyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5h). Prepared viaProcedure A from 6-chloro-1-hexene (2h, 0.200 mmol) and obtained as a yellow oil (46.9 mg,65%).1H NMR (400 MHz, CD3CN) δ 8.99–8.87 (m, 2H), 8.44 (t, J = 7.8 Hz, 1H), 8.14–7.96 (m,2H),3.76 (t, J = 6.5 Hz, 2H), 3.27 (dq, J = 8.5, 5.8 Hz, 1H), 3.17 (dd, J = 8.5, 2.7 Hz, 1H), 2.87(dd,J = 5.6, 2.7 Hz, 1H), 2.03–1.89 (m, 3H), 1.88–1.72 (m, 3H).19F NMR (377 MHz, CD3CN) δ –79.3.13C NMR (101 MHz, CD3CN) δ 144.0, 141.2, 129.3, 122.0 (q, J = 320.7 Hz), 47.5, 45.8, 41.0,32.8, 30.8, 24.3. HRMS-ESI+ (m / z): [M]+ calcd. for C11H16ClN2+, 211.0997, 213.0967;found,211.0994, 213.0963. 1-(2-(4-(Benzoyloxy)butyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5i). Preparedvia Procedure A from hex-5-en-1-yl benzoate (2i, 0.200 mmol) and obtained as ayellow oil (64.3mg, 72%). 1H NMR (500 MHz, CD3CN) δ 8.78 (d, J = 6.2 Hz, 2H), 8.32 (t, J =7.8 Hz, 1H), 8.03(d, J = 8.4 Hz, 2H), 7.94 (t, J = 7.3 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.8 Hz, 2H), 4.35(t, J = 6.4 Hz, 2H), 3.21–3.12 (m, 1H), 3.05 (dd, J = 8.4, 2.7 Hz, 1H), 2.78 (dd,J = 5.7, 2.7 Hz, 1H),1.90–1.82 (m, 3H), 1.81–1.69 (m, 3H).19F NMR (377 MHz, CD3CN) δ –79.3. 13C NMR (126 MHz,CD3CN) δ 167.2, 144.0, 141.2, 134.0, 131.4, 130.2, 129.5, 129.3, 122.0 (q, J = 320.5 Hz), 65.4, 47.7,41.0, 31.2, 29.0, 23.6. HRMS-ESI+ (m / z): [M]+ calcd. for C18H21N2O2+,297.1598; found, 297.1591.1-(2-(4-Cyanobutyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5j). Prepared viaProcedure A from hept-6-enenitrile (2j, 0.300 mmol) and obtained as a yellow solid (93.8mg,89%). 1H NMR (400 MHz, CD3CN) δ 8.79 (d, J = 5.3 Hz, 2H), 8.33 (t, J = 7.8 Hz, 1H), 7.96(t,J = 7.1 Hz, 2H), 3.16 (dq, J = 10.6, 5.7, 4.7 Hz, 1H), 3.05 (dd, J = 8.5, 2.6 Hz, 1H), 2.77 (dd, J = 5.8, 2.6 Hz, 1H), 2.45 (t, J = 6.4 Hz, 2H), 1.87–1.77 (m, 1H), 1.79–1.62 (m, 5H).19F NMR (376 MHz, CD3CN) δ –79.3.13C NMR (101 MHz, CD3CN) δ 144.1, 141.2, 129.3, 122.0 (q, J = 320.5 Hz), 121.1, 47.3, 41.0, 30.7, 26.0, 25.7, 17.3. HRMS-ESI+(m / z): [M]+calcd. for C12H16N3+, 202.1339; found, 202.1334. 1-(2-(4-Azidobutyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5k). Prepared viaProcedure B from 6-azidohex-1-ene (2k, 0.200 mmol) and obtained as a yellow oil (48.5 mg,66%).1H NMR (500 MHz, CD3CN) δ 8.84–8.73 (m, 2H), 8.32 (t, J = 7.8 Hz, 1H), 7.95 (t, J = 7.2Hz,2H), 3.37 (t, J = 6.0 Hz, 2H), 3.13 (dq, J = 7.8, 6.1 Hz, 1H), 3.03 (dd, J = 8.4, 2.7 Hz, 1H), 2.77(dd,J = 5.7, 2.7 Hz, 1H), 1.80 (p, J = 6.7 Hz, 1H), 1.75–1.60 (m, 5H).19F NMR (376 MHz, CD3CN) δ – 79.3.13C NMR (126 MHz, CD3CN) δ 144.1, 141.2, 129.3, 51.8, 47.6, 41.0, 31.1, 29.1, 24.2.HRMS-ESI+ (m / z): [M]+ calcd. for C11H16N5+, 218.1400; found, 218.1397.1-(2-Cyclohexylaziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5l). Prepared viaProcedure B from vinylcyclohexene (2l, 0.200 mmol) and obtained as a yellow oil (44.3 mg,63%).1H NMR (400 MHz, CD3CN) δ 8.76 (d, J = 5.5 Hz, 2H), 8.32 (t, J = 7.8 Hz, 1H), 7.95 (t, J =7.3Hz, 2H), 3.03 (dd, J = 8.5, 2.5 Hz, 1H), 2.97 (td, J = 8.1, 7.6, 5.4 Hz, 1H), 2.82 (dd, J = 5.5, 2.5 Hz,1H), 2.05–1.98 (m, 1H), 1.86–1.75 (m, 3H), 1.75–1.66 (m, 1H), 1.45–1.11 (m, 6H).19F NMR(376MHz, CD3CN) δ –79.3.13C NMR (126 MHz, CD3CN) δ 144.0, 141.2, 129.4, 122.0 (q, J = 320.8 Hz), 52.3, 40.0, 39.7, 30.9, 29.6, 26.7, 26.2. HRMS-ESI+(m / z): [M]+calcd. for C13H19N2+, 203.1543; found, 203.1540. 1-(2-(2-(Benzoyloxy)ethyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5m). Preparedvia Procedure A from but-3-en-1-yl benzoate (2m, 0.200 mmol) and obtained as acolorless oil(50.8 mg, 61%). 1H NMR (500 MHz, CDCl3) δ 8.94 (d, J = 5.6 Hz, 2H), 8.25 (t, J =7.8 Hz, 1H),8.03 (d, J = 6.9 Hz, 2H), 7.92 (t, J = 7.3 Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.8 Hz, 2H), 4.69 (ddd, J = 11.9, 7.7, 4.4 Hz, 1H), 4.55 (ddd, J = 11.4, 6.7, 4.7 Hz, 1H), 3.61 (tt, J = 8.1, 5.2 Hz,1H), 3.48 (dd, J = 8.5, 2.7 Hz, 1H), 2.78 (dd, J = 1H), 2.29 (ddt, J = 15.3,7.9, 4.8 Hz,1H), 2.13 (dtd, J = 14.9, 7.0, 4.4 Hz, 1H).19F NMR (377 MHz, CDCl3) δ –78.4.13C NMR (126 MHz, CDCl3) δ 166.8, 142.9, 140.4, 133.6, 129.8, 129.7, 128.8, 128.7, 120.7 (q, J = 319.9 Hz),62.1, 44.7, 40.2, 30.9. HRMS-ESI+ (m / z): [M]+ calcd. for C16H17N2O2+, 269.1285;found,269.12853. 1-(2-Benzylaziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5n). Prepared via ProcedureB from allylbenzene (2n, 0.300 mmol) and obtained as a yellow oil (54.6 mg, 50%).1H NMR (400MHz, CD3CN) δ 8.60 (d, J = 6.0 Hz, 2H), 8.29 (t, J = 7.8 Hz, 1H), 7.97–7.81 (m,2H), 7.48–7.21(m, 5H), 3.42–3.33 (m, 1H), 3.14–3.03 (m, 3H), 2.87 (dd, J = 5.7, 2.9 Hz, 1H). These spectral data are well-matched to those reported in the literature [2]. 1-(2-Phenethylaziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5o). Prepared viaProcedure A from but-3-en-1-ylbenzene (2o, 0.3 mmol) and obtained as a yellow solid (81.6mg,73%). 1H NMR (500 MHz, CDCl3) δ 8.48 (d, J = 6.5 Hz, 2H), 8.14 (t, J = 7.8 Hz, 1H), 7.80 (t,J =7.3 Hz, 2H), 7.33–7.03 (m, 2H), 3.31–3.11 (m, 2H), 3.03–2.78 (m, 2H), 2.61–2.53 (m, 1H),2.16–1.69 (m, 2H). 19F NMR (377 MHz, CDCl3) δ –78.3. 13C NMR (126 MHz, CDCl3) δ 142.7,140.2,139.3, 128.9, 128.8, 128.7, 126.7, 120.7 (q, J = 319.5 Hz), 46.9, 40.2, 32.7, 32.4. HRMS-ESI+(m / z): [M]+ calcd. for C15H17N2+, 225.1386; found, 225.1385.1-(2-(3-Phenylpropyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5p). Prepared viaProcedure B from pent-4-en-1-ylbenzene (2p, 0.200 mmol) and obtained as a yellow oil(35.5 mg,46%). 1H NMR (500 MHz, CDCl3) δ 8.55 (d, J = 6.5 Hz, 2H), 8.21 (t, J = 7.8 Hz, 1H),7.87 (t, J= 7.3 Hz, 2H), 7.40–7.10 (m, 5H), 3.38–3.18 (m, 2H), 3.10–2.85 (m, 2H), 2.67–2.60(m, 1H),2.23–1.76 (m, 2H).19F NMR (377 MHz, CD3CN) δ –79.3. 13C NMR (126 MHz, CD3CN)δ 144.0,143.0, 141.2, 129.4, 129.4, 129.3, 126.9, 122.1 (q, J = 320.7 Hz), 47.7, 41.1, 36.0, 31.3,29.0.HRMS-ESI+(m / z): [M]+calcd. for C16H19N2+, 239.1543; found, 239.1530. 1-(6-(tert-Butoxycarbonyl)-1,6-diazaspiro[2.5]octan-1-yl)pyridin-1-ium trifluoromethanesulfonate (5q). Prepared via Procedure B from tert-butyl 4-methylenepiperidine-1-carboxylate (2q, 0.200mmol) and obtained as a yellow oil (58.9 mg,67%). 1H NMR (500 MHz, CD3CN) δ 8.72 (d, J =5.5 Hz, 2H), 8.36 (t, J = 7.8 Hz, 1H), 7.99 (t, J =7.3 Hz, 2H), 4.13 (t, J = 15.4 Hz, 2H), 3.09 (dd, J= 3.5, 1.1 Hz, 1H), 3.01 (dd, J = 3.5, 1.9 Hz, 1H), 2.20 (td, J = 12.7, 4.6 Hz, 1H), 2.13 (d, J = 16.4Hz, 1H), 1.80 (tdd, J = 11.8, 4.8, 2.0 Hz, 1H), 1.45(s, 11H), 0.73 (dd, J = 12.5, 2.7 Hz, 1H). 19FNMR (376 MHz, CD3CN) δ –79.3.13C NMR (126 MHz, CD3CN) δ 155.2, 144.0, 141.4, 129.4, 122.1 (q, J = 320.9 Hz), 80.4, 53.2, 45.1, 30.1, 28.5, 28.5. HRMS-ESI+(m / z): [M]+calcd. for C16H24N3O2+, 290.1863; found, 290.1855. 1-(2-(4-Vinylphenethyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5r). Prepared viaProcedure B from 1-(but-3-en-1-yl)-4-vinylbenzene (2r, 0.300 mmol) and obtained as ayellowoil (78.1 mg, 65%). 1H NMR (500 MHz, CD3CN) δ 8.91 (dd, J = 5.2, 1.9 Hz, 2H), 8.38 (t,J = 7.8Hz, 1H), 8.00 (t, J = 7.3 Hz, 2H), 7.37 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 7.6 Hz, 2H), (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.04 (dq, J = 17.2, 1.8 Hz, 1H), 4.97 (dq, J = 10.3, 1.5 Hz, 1H), 4.20(ddd, J = 8.1, 5.7, 2.2 Hz, 1H), 3.49 (ddd, J = 8.9, 3.2, 1.3 Hz, 1H), 3.20 (dd, J = 5.8, 3.1 Hz,1H),2.74 (t, J = 7.8 Hz, 2H), 2.46–2.31 (m, 2H).19F NMR (377 MHz, CD3CN) δ –79.2.13C NMR (126 MHz, CD3CN) δ 144.4, 144.0, 141.2, 139.0, 132.7, 129.8, 129.4, 127.9, 122.0 (d, J = 320.6 Hz), 115.5, 48.2, 42.8, 35.9, 35.4. HRMS-ESI+(m / z): [M]+calcd. for C17H19N2+, 251.1543; found, 251.1536. 1-(2-(4-((2-(4-Isobutylphenyl)propanoyl)oxy)butyl)aziridin-1-yl)pyridin-1-iumtrifluoromethanesulfonate (5s). Prepared via Procedure A from 2s (0.200 mmol) andobtained as acolorless oil (49.0 mg. 46%). 1H NMR (500 MHz, CDCl3) δ 8.78 (dd, J = 5.2, 1.6Hz, 2H), 8.27(t, J = 7.8 Hz, 1H), 7.97 (t, J = 7.3 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 6.5 Hz, 2H), 4.11 (td, J = 6.5, 1.9 Hz, 2H), 3.70 (q, J = 7.1 Hz, 1H), 3.41 (s, 2H), 2.64 (dd, J = 4.8, 3.2 Hz, 1H), 2.42 (dd, J = 7.2, 4.6 Hz, 2H), 1.83 (dtt, J = 13.6, 6.8, 3.6 Hz, 1H), 1.76–1.65 (m, 4H), 1.60–1.52 (m,2H), 1.49 (d, J = 7.1 Hz, 3H), 0.88 (dd, J = 6.6, 1.7 Hz, 6H).19F NMR (377 MHz,CDCl3) δ –78.4. 13C NMR (126 MHz, CDCl3) δ 175.0, 142.7, 140.7, 140.2, 137.9, 129.5, 128.8,127.3, 120.7(q, J = 320.0 Hz), 64.2, 47.2, 45.3, 45.2, 40.4, 30.7, 30.3, 28.3, 23.0, 22.5, 18.7.HRMS-ESI+(m / z): [M]+calcd. for C24H33N2O2+, 381.2537; found, 381.2533. 1-(2-(4-((3-(4,5-Diphenyloxazol-2-yl)propanoyl)oxy)butyl)aziridin-1-yl)pyridin-1-iumtrifluoromethanesulfonate (5t). Prepared via Procedure B from 2t (0.300 mmol) andobtained as acolorless oil (40.9 mg, 22%). 1H NMR (500 MHz, CD3CN) δ 8.76–8.68 (m, 2H),8.36–8.21 (m,1H), 7.99–7.85 (m, 2H), 7.62–7.49 (m, 4H), 7.48–7.26 (m, 6H), 4.14 (t, J = 6.3 Hz, 2H), 3.13 (t, J = 7.0 Hz, 2H), 3.07–2.99 (m, 1H), 2.95 (ddd, J = 8.4, 5.3, 2.6 Hz, 1H), 2.88 (t, J = 7.1 Hz, 2H),2.69 (dd, J = 5.7, 2.6 Hz, 1H), 1.81–1.67 (m, 3H), 1.66–1.53 (m, 3H).19F NMR(377 MHz,CD3CN) δ –79.3. 13C NMR (126 MHz, CD3CN) δ 173.0, 163.4, 146.2, 144.0, 141.2,135.7, 133.5,129.9, 129.8, 129.7, 129.5, 129.3, 129.1, 128.5, 127.4, 122.1 (q, J = 321.2 Hz),65.0, 47.6, 40.9,31.5, 31.1, 28.9, 24.1, 23.5. HRMS-ESI+ (m / z): [M]+ calcd. for C29H30N3O3+,468.2282; found,468.2276. 1-(2-(2-((N-(tert-Butoxycarbonyl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1- yl)phenyl)sulfonamido)ethyl)aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5u). Prepared viaProcedure A from 2u (0.300 mmol) and obtained as a yellow solid (113 mg,48%) containing15% of the corresponding imine byproduct 5u’.( Resonances at 8.74, 8.53, 8.36, and 8.11 ppmindicate the presence of the imine byproduct 5u’.) 1H NMR (500 MHz, CD3CN)δ 8.86 (d, J = 5.7Hz, 2H), 8.34 (t, J = 7.8 Hz, 1H), 7.97 (t, J = 7.3 Hz, 2H), 7.92 (d, J = 8.8 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 7.31–7.14 (m, 4H), 6.93 (s, 1H), 4.21–4.05 (m, 2H), 3.28 (dq, J = 8.5, 6.3 Hz, 1H), 3.11(dd, J = 8.4, 2.8 Hz, 1H), 2.83 (dd, J = 5.6, 2.8 Hz, 1H), 2.34 (s, 3H), 2.26 (dq, J= 13.7, 7.2 Hz,1H), 2.08 (dq, J = 14.1, 7.1 Hz, 1H), 1.30 (s, 9H).19F NMR (376 MHz, CD3CN) δ –62.8, –79.2.13C NMR (126 MHz, CD3CN) δ 178.4, 151.6, 146.7, 144.3, 144.1, 144.0, 141.4,140.8, 140.4,130.4, 129.9, 129.6, 129.3, 126.7, 122.4 (q, J = 268.0 Hz), 122.1 (q, J = 320.7 Hz),107.2, 86.1, 45.3,45.2, 40.9, 32.7, 28.0, 21.2. HRMS-ESI+ (m / z): [M]+ calcd. for C31H33F3N5O4S+,628.2200; found,628.2190. (E)-1-(3-(5-Acetoxy-3-methylpent-3-en-1-yl)-2,2-dimethylaziridin-1-yl)pyridin-1-iumtrifluoromethanesulfonate (5v). Prepared via Procedure A from geranyl acetate (2v, 0.200mmol)and obtained as a yellow oil (50.5 mg, 58%). 1H NMR (400 MHz, CD3CN) δ 8.64 (d, J =6.6 Hz,2H), 8.34 (t, J = 7.8 Hz, 1H), 7.98 (t, J = 7.2 Hz, 2H), 5.57–5.24 (m, 1H), 4.67–4.43 (m, 2H), 3.02(t, J = 6.8 Hz, 1H), 2.36 (t, J = 7.5 Hz, 2H), 1.97 (s, 4H), 1.91–1.82 (m, 1H), 1.76 (s,3H), 1.45 (s,3H), 1.10 (s, 3H). 19F NMR (376 MHz, CD3CN) δ –79.3. 13C NMR (101 MHz, CD3CN)δ 171.6,143.6, 141.5, 141.1, 129.3, 122.0 (q, J = 320.7 Hz), 121.0, 61.7, 56.5, 53.8, 37.1, 25.9,21.1, 20.6,19.6, 16.3. HRMS-ESI+ (m / z): [M]+ calcd. for C17H25N2O2+, 289.1911; found,289.1906.(E)-1-(3-(5-(1,3-Dioxoisoindolin-2-yl)-3-methylpent-3-en-1-yl)-2,2-dimethylaziridin-1- yl)pyridin-1-ium trifluoromethanesulfonate (5w). Prepare via Procedure A from (E)-2-(3,7-dimethylocta-2,6-dien-1-yl)isoindoline-1,3-dione (2w, 0.200 mmol) and obtained as a whitesolid(60.1 mg, 57%). 1H NMR (400 MHz, CD3CN) δ 8.65–8.55 (m, 2H), 8.28 (t, J = 7.6 Hz, 1H),7.94(t, J = 7.3 Hz, 2H), 7.77 (s, 4H), 5.40 (ddq, J = 6.7, 5.4, 1.4 Hz, 1H), 4.23 (dt, J = 9.5, 4.8 Hz, 2H),3.00 (t, J = 6.8 Hz, 1H), 2.46–2.27 (m, 2H), 2.19 (s, 1H), 1.84 (m, 4H), 1.43 (s, 3H), 1.04(s, 3H).19F NMR (377 MHz, CD3CN) δ –79.3.13C NMR (126 MHz, CD3CN) δ 169.0, 143.5, 141.0,139.6,135.1, 133.1, 129.2, 123.8, 122.0 (d, J = 320.7 Hz), 120.9, 56.4, 53.6, 37.0, 36.4, 25.6,20.5, 19.6,16.3. HRMS-ESI+(m / z): [M]+calcd. for C23H26N3O2+, 376.2020; found, 376.2016. 1-((1R,10S)-4,12,12-Trimethyl-9-methylene-5-azatricyclo[8.2.0.04,6]dodecan-5-yl)pyridin-1- ium trifluoromethanesulfonate (5x). Prepared via Procedure B from β-caryophyllene (2x, 0.200mmol) and obtained as a yellow solid (74.6 mg, 84%). This was also scaled up using1.00 mmolof 2x, affording 369 mg of the product in 83% yield. 1H NMR (400 MHz, CD3CN) δ8.66 (d, J =5.8 Hz, 2H), 8.32 (t, J = 7.8 Hz, 1H), 7.95 (t, J = 7.3 Hz, 2H), 5.04 (d, J = 1.7 Hz, 1H), 4.93 (d, J = 1.8 Hz, 1H), 3.20 (dd, J = 11.3, 4.1 Hz, 1H), 2.75 (q, J = 9.6 Hz, 1H), 2.64 (ddt, J = 13.4, 7.9, 4.1 Hz, 1H), 2.44 (ddd, J = 13.1, 8.8, 4.1 Hz, 1H), 2.24–2.14 (m, 1H), 2.00 (dt, J = 12.4, 3.7 Hz, 1H),1.76 (td, J = 9.6, 1.6 Hz, 1H), 1.68–1.59 (m, 4H), 1.56–1.49 (m, 1H), 1.40 (s, 3H),1.00 (s, 3H),0.92 (s, 3H), 0.29 (td, J = 12.3, 5.4 Hz, 1H).19F NMR (376 MHz, CD3CN) δ –79.3.13C NMR(101 MHz, CD3CN) δ 152.3, 143.4, 141.2, 129.2, 122.1 (q, J = 320.9 Hz), 113.8, 57.4,55.3, 49.9,49.0, 40.0, 35.2, 35.0, 30.3, 30.1, 29.7, 26.9, 21.6, 18.3. HRMS-ESI+(m / z): [M]+calcd.forC20H29N2+, 297.2325; found, 297.2320. 1-((3S,6aR,6bS,9aS,11aS,11bR)-3-Methoxy-9a,11b-dimethyl-9-oxohexadecahydro-5H- cyclopenta[1,2]phenanthro[8a,9-b]azirin-5-yl)pyridin-1-ium trifluoromethanesulfonate (5y). Prepared via Procedure A from O-methyl dehydroepiandrosterone (2y, 0.300 mmol) andobtained as a yellow powder (133 mg, 82%). 1H NMR (500 MHz, CDCl3) δ 8.88 (s, 2H), 8.33(t,J = 8.1 Hz, 1H), 8.07 (t, J = 7.2 Hz, 2H), 3.95 (s, 1H), 3.52–3.43 (m, 1H), 3.18 (s, 3H), 2.64–2.52(m, 1H), 2.50–2.36 (m, 1H), 2.15–1.97 (m, 2H), 1.94–1.73 (m, 3H), 1.61 (dt, J = 13.0, 9.5Hz, 3H),1.55–1.40 (m, 5H), 1.31–1.13 (m, 5H), 0.94–0.75 (m, 5H).19F NMR (377 MHz, CDCl3) δ –78.3.13C NMR (126 MHz, CDCl3) δ 220.3, 142.4, 140.5, 128.8, 120.9 (q, J = 320.4 Hz), 59.0,56.1, 52.9,51.4, 49.1, 47.4, 36.2, 35.8, 34.9, 33.6, 31.5, 30.5, 28.9, 26.0, 21.7, 21.6, 20.4, 13.6.HRMS-ESI+(m / z): [M]+calcd. for C25H35N2O2+, 395.2693; found, 395.2687. (R)-1-(2-Methyl-2-(4-methyl-5-oxocyclohex-3-en-1-yl)aziridin-1-yl)pyridin-1-iumtrifluoromethanesulfonate (5z). Prepare via Procedure A from (R)-carvone (2z, 0.300 mmol)andobtained as a yellow oil (47.1 mg, 40%). 1H NMR (500 MHz, CD3CN) δ 8.67–8.58 (m, 2H),8.44–8.33 (m, 1H), 8.12–7.91 (m, 2H), 6.94–6.61 (m, 1H), 3.06 (d, J = 3.7 Hz, 1H), 2.97 (dd, J = 3.8,2.3 Hz, 1H), 2.61 (dddd, J = 27.5, 15.5, 3.6, 1.7 Hz, 1H), 2.55–2.38 (m, 2H), 2.38–2.21 (m,2H),1.79–1.71 (m, 3H), 1.10 (s, 3H). 19F NMR (377 MHz, CD3CN) δ –79.3. 13C NMR (126 MHz,CD3CN) δ 198.6, 198.5, 146.4, 144.8, 144.7, 143.9, 143.0, 141.4, 141.4, 140.2, 136.1, 136.0, 129.5, 129.5, 122.0 (q, J = 321.0 Hz), 54.0, 53.9, 44.6, 42.1, 42.0, 40.5, 40.2, 28.5, 28.2, 15.7, 15.7, 14.9, 14.8. HRMS-ESI+(m / z): [M]+calcd. for C15H19N2O+, 243.1492; found, 243.1490. (R)-1-((2-(4-Methyl-5-oxocyclohex-3-en-1-yl)propylidene)amino)pyridin-1-iumtrifluoromethanesulfonate (5z’). Prepared via Procedure A from (R)-carvone (0.300 mmol)andobtained as a yellow oil (21.6 mg, 18%). 1H NMR (400 MHz, CDCl3) δ 8.94 (d, J = 6.2 Hz,2H),8.77 (d, J = 5.8 Hz, 1H), 8.52 (t, J = 7.6 Hz, 1H), 8.13 (t, J = 7.0 Hz, 2H), 6.76 (s, 1H), 3.03–2.78(m, 1H), 2.57 (dd, J = 21.6, 15.9 Hz, 3H), 2.32 (qd, J = 11.3, 5.1 Hz, 2H), 1.75 (s, 3H), 1.32(t, J =6.6 Hz, 3H). 19F NMR (376 MHz, CDCl3) δ –78.5. 13C NMR (126 MHz, CDCl3) δ 198.9,180.3,145.2, 144.8, 139.4, 135.8, 129.0, 120.6 (q, J = 320.0 Hz), 42.0, 41.3, 37.9, 30.1, 15.7,13.5.HRMS-ESI+(m / z): [M]+calcd. for C15H19N2O+, 243.1492; found, 243.1490. 1-(Aziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5aa). Prepared via Procedure C fromethylene and 3 (0.600 mmol), and obtained as a yellow oil (78.0 mg, 48%).1H NMR(400 MHz,CD3CN) δ 9.01 (d, J = 6.0 Hz, 2H), 8.35 (t, J = 7.8 Hz, 1H), 8.09–7.75 (m, 2H), 3.03–2.96 (m, 2H), 2.88–2.80 (m, 2H).19F NMR (377 MHz, CD3CN) δ –79.3.13C NMR (101 MHz, CD3CN) δ144.1, 141.6, 129.3, 35.0. HRMS-ESI+ (m / z): [M]+ calcd. for C7H9N2+, 121.0760;found,121.0762. 1-(2-Methylaziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5ab). Prepared via Procedure Cfrom propylene and 3 (0.200 mmol), and obtained as a yellow oil (21.7 mg, 38%)containing 13%of the imine byproduct 5ab’. 1H NMR (400 MHz, CD3OD) δ 9.13 (d, J = 5.7 Hz,2H), 8.40 (t, J =7.8 Hz, 1H), 8.10–7.87 (m, 2H), 3.30–3.22 (m, 1H), 3.15 (dd, J = 8.4, 2.6 Hz,1H), 2.74 (dd, J =5.8, 2.5 Hz, 1H), 1.53 (d, J = 5.7 Hz, 3H).19F NMR (377 MHz, CD3OD) δ –80.1.13C NMR (101 MHz, CD3OD) δ 144.1, 141.7, 129.5, 121.8 (q, J = 318.5 Hz), 44.0, 41.9, 16.9. HRMS-ESI+(m / z): [M]+calcd. for C8H11N2+, 135.0917; found, 135.0915. 1-(2,2-Dimethylaziridin-1-yl)pyridin-1-ium trifluoromethanesulfonate (5ac). Prepared viaProcedure C from isobutylene and 3 (0.200 mmol), and obtained as a yellow oil (20.7 mg,35%)containing 33% of imine byproduct 5ac’. 1H NMR (400 MHz, CD3CN) δ 8.71 (d, J = 5.9Hz, 2H),8.35 (t, J = 7.8 Hz, 1H), 7.99 (t, J = 7.3 Hz, 2H), 2.97 (d, J = 3.5 Hz, 1H), 2.91 (d, J = 3.7Hz, 1H),1.50 (s, 3H), 1.13 (s, 3H).19F NMR (376 MHz, CD3CN) δ –79.3.13C NMR (101 MHz, CD3CN)δ 182.5, 146.1, 143.5, 141.4, 140.1, 129.5, 129.3, 121.9 (q, J = 320.5 Hz), 49.6, 46.5,33.4, 24.1,19.1, 18.4. (Extra signals are due to the imine byproduct.) HRMS-ESI+(m / z): [M]+ calcd. forC9H13N2+, 149.1073; found, 149.1071. EXAMPLE 7 B.4 Cross-Coupling of Pyridinium AziridinesA 20- phosphate(2.8equiv.), aryl boronic acid (11, 2.4 equiv.), and pyridinium aziridine (5, 1.0 equiv.). In anN2filleddry box, a solution of 2,4,6-collidine in acetonitrile (0.10 M, 1.0 equiv.) was added tothe reactionvial. With stirring, the reaction mixture was heated to 65 ℃ for 36 h. After cooling to 23 ℃,the reaction mixture was transferred to a centrifuge tube and centrifuged at4000 rpm for 4 min.The supernatant was decanted. The residue was washed with CH2Cl2 and the combinedsupernatants were concentrated under reduced pressure and the crude mixture was purified as indicated below to afford the indicated compounds.7-(3,5-Bis(trifluoromethyl)phenyl)-7-azabicyclo[4.1.0]heptane (12a). Prepared from 5a(0.200mmol), purified on deactivated silica gel column (1% to 10% Et2O in hexanes) (Silica gel (20 mL) was wet-packed with hexanes. 1% Et3N in hexanes (20 mL) was passed through the column, followed by 100% hexanes (20 mL). The crude mixture dried in neutral alumina was dry-loaded on the column.), and obtained as a white solid (31.1 mg, 50%).1H NMR (499 MHz, CDCl3) δ 7.40(s, 1H), 7.33 (s,2H), 2.46–2.38 (m, 2H), 2.07 (dt, J = 13.3, 6.5 Hz, 2H), 1.99–1.89 (m, 2H), 1.55–1.44 (m, 2H),1.38–1.28 (m, 2H). 19F NMR (470 MHz, CDCl3) δ –63.0. 13C NMR (126 MHz,CDCl3) δ 157.2,132.3 (q, J = 33.0 Hz), 123.5 (q, J = 272.6 Hz), 120.6, 115.3, 39.7, 24.5, 20.2.HRMS-ESI+(m / z):[M+1]+ calcd. for C14H14F6N+, 310.1025; found, 310.1020.tert-Butyl 1-(3,5-bis(trifluoromethyl)phenyl)-1,6-diazaspiro[2.5]octane-6-carboxylate (12b). Prepared from 5q (0.100 mmol), purified on deactivated silica gel column (10% EtOAc inhexanes), and obtained as a white solid (14.7 mg, 35%).1H NMR (500 MHz, CDCl3) δ 7.45 (s,1H),7.28 (s, 2H), 4.12 (s, 2H), 2.99 (t, J = 12.2 Hz, 2H), 1.91 (td, J = 12.2, 4.2 Hz, 2H), 1.48 (s,9H),1.12 (d, J = 13.2 Hz, 2H). 19F NMR (376 MHz, CDCl3) δ –63.0. 13C NMR (126 MHz, CDCl3)δ154.8, 151.9, 132.4 (q, J = 33.1 Hz), 123.4 (q, J = 272.8 Hz), 120.8, 115.7, 80.2, 44.9, 39.2,33.3,28.6. HRMS-ESI+(m / z): [M+1]+calcd. for C19H23F6N2O2+, 425.1658; found, 425.1647.exo-3-(3,5-Bis(trifluoromethyl)phenyl)-3-azatricyclo[3.2.1.02,4]octane (12c). Prepared from5e(0.150 mmol), purified on deactivated silica gel column (1% to 10% Et2O in hexanes), and obtainedas a white solid (31.4 mg, 65%). 1H NMR (400 MHz, CDCl3) δ 7.35 (s, 1H), 7.32 (s,2H), 2.60(s, 2H), 2.40 (s, 2H), 1.61–1.44 (m, 3H), 1.28–1.17 (m, 2H), 0.90 (d, J = 10.2 Hz, 1H).19F NMR(376 MHz, CDCl3) δ –63.1.13C NMR (126 MHz, CDCl3) δ 154.7, 132.3 (q, J = 33.1 Hz),123.5 (q,J = 272.7 Hz), 121.0, 42.1, 36.4, 29.1, 26.2. HRMS-ESI+(m / z): [M+1]+calcd. ForC15H14F6N+,322.1025; found, 322.1020. The spectroscopic data didn’t match those reportedin literature, butXRD analysis unambiguously characterized the structure of 12c. (E)-5-(1-(3,5-Bis(trifluoromethyl)phenyl)-3,3-dimethylaziridin-2-yl)-3-methylpent-2-en-1-yl acetate (12d). Prepared from 5v (0.200 mmol), purified on neutral alumina column (0% to 5%EtOAc in hexanes), and obtained as a colorless oil (35.9 mg, 42%).1H NMR (400 MHz,CDCl3)δ 7.41 (s, 1H), 7.18 (s, 2H), 5.47 (t, J = 6.7 Hz, 1H), 4.61 (d, J = 7.0 Hz, 2H), 2.31 (td, J =7.6, 3.4Hz, 2H), 2.03 (s, 3H), 2.00 (dd, J = 7.4, 5.7 Hz, 1H), 1.86–1.70 (m, 5H), 1.37 (s, 3H),1.00 (s,3H). 19F NMR (377 MHz, CDCl3) δ –63.0. 13C NMR (101 MHz, CDCl3) δ 171.2, 153.0,141.2,132.2 (q, J = 33.1 Hz), 123.5 (q, J = 272.7 Hz), 120.4, 119.5, 115.1, 61.3, 50.6, 44.1, 37.7,27.1, 22.0,21.1,(Two resonances for methyl carbons overlap at 21.1, which is confirmed by HSQC analysis.)16.6. HRMS-ESI+ (m / z): [M+1]+ calcd. for C20H24F6NO2+, 424.1706; found,424.1697.(1R,10S)-5-(3,5-Bis(trifluoromethyl)phenyl)-4,12,12-trimethyl-9-methylene-5- azatricyclo[8.2.0.04,6]dodecane (12e). Prepared from 5x (0.200 mmol), purified on neutralalumina column (100% hexanes), and obtained as a colorless oil (57.8 mg, 67%).1H NMR(500MHz, CDCl3) δ 7.39 (s, 1H), 7.17 (s, 2H), 5.02 (d, J = 1.7 Hz, 1H), 4.93 (d, J = 1.6 Hz, 1H),2.66(dd, J = 19.4, 8.6 Hz, 1H), 2.44 (ddt, J = 11.5, 6.7, 3.8 Hz, 2H), 2.24–2.12 (m, 2H), 1.92 (dt, J =13.1, 3.6 Hz, 1H), 1.70–1.58 (m, 5H), 1.55–1.46 (m, 1H), 1.32 (s, 3H), 1.00 (s, 3H), 0.93 (s,3H),0.36 (td, J = 12.8, 4.8 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ –63.0. 13C NMR (126 MHz,CDCl3) δ 132.2 (q, J = 32.9 Hz), 123.5 (q, J = 272.6 Hz), 120.3, 114.9, 112.7, 51.3, 51.1, 49.0, 45.7, 39.5, 37.0, 34.3, 31.3, 31.0, 30.0, 27.2, 21.7, 19.2. HRMS-ESI+(m / z): [M+1]+calcd. for C23H28F6N+, 432.2120; found, 432.2105. (3S,6aR,6bS,9aS,11aS,11bR)-5-(3,5-Bis(trifluoromethyl)phenyl)-3-methoxy-9a,11b- dimethylhexadecahydro-9H-cyclopenta[1,2]phenanthro[8a,9-b]azirin-9-one (12f). Prepared from 5y (0.150 mmol), purified on neutral alumina column (10% EtOAc in hexanes), and obtained as a white solid (26.5 mg, 33%).1H NMR (400 MHz, CDCl3) δ 7.41 (s, 1H), 7.21 (s, 2H), 3.39 (dq, J = 10.6, 5.8 Hz, 1H), 3.23 (s, 3H), 2.54–2.41 (m, 2H), 2.34 (dt, J = 13.6, 3.1 Hz,1H), 2.16–1.93 (m, 2H), 1.92–1.71 (m, 5H), 1.65–1.33 (m, 7H), 1.27–1.15 (m, 5H), 0.84 (s, 4H),0.65(dd, J = 13.2, 5.7 Hz, 1H).19F NMR (377 MHz, CDCl3) δ –63.0.13C NMR (101 MHz, CDCl3)δ220.8, 151.9, 132.3 (q, J = 33.0 Hz), 123.5 (q, J = 272.7 Hz), 120.1, 115.1, 77.4, 55.9, 51.7, 50.2,49.6, 47.7, 47.3, 36.0, 35.9, 35.0, 31.8, 31.0, 30.5, 26.2, 21.9, 21.8, 21.0, 13.7. (The signalat 77.4ppm overlapped with CDCl3signal and was confirmed by HSQC.) HRMS-ESI+(m / z): [M+1]+calcd. for C28H34F6NO2+, 530.2488; found, 530.2483. Methyl exo-2-(1-(4-(3-azatricyclo[3.2.1.02,4]octan-3-yl)benzoyl)-5-methoxy-2-methyl-1H-indol-3- yl)acetate (12g). Prepared from 5e (0.150 mmol), purified on neutral alumina column (10%EtOAc in hexanes), and obtained as a yellow solid (29.8 mg, 45%).1H NMR(400 MHz, CDCl3)δ 7.59 (d, J = 8.6 Hz, 2H), 7.01–6.93 (m, 3H), 6.89 (d, J = 9.0 Hz, 1H), 6.63(dd, J = 9.0, 2.6 Hz,1H), 3.84 (s, 3H), 3.70 (s, 3H), 3.67 (s, 2H), 2.58 (s, 2H), 2.42–2.38 (m, 5H), 1.64–1.43 (m, 3H),1.24 (dd, J = 7.6, 2.4 Hz, 2H), 0.90 (d, J = 9.9 Hz, 1H).13C NMR (101 MHz,CDCl3) δ 171.7,169.1, 158.3, 155.8, 136.3, 131.8, 131.3, 130.4, 127.9, 120.8, 115.0, 111.5,101.1, 55.9, 52.2,41.8, 36.5, 30.4, 29.2, 26.3, 13.2. HRMS-ESI+(m / z): [M+1]+calcd. forC27H29N2O4+, 445.2122;found, 445.2118. Ethyl 4-(2-(2-((N-(tert-butoxycarbonyl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1- yl)phenyl)sulfonamido)ethyl)aziridin-1-yl)benzoate (12h). Prepared from 5u (0.107 mmol),purified on deactivated silica gel column (17% to 25% EtOAc in hexanes), and obtained as awhitesolid (7.3 mg, 10%). 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.6 Hz, 2H), 7.89 (d, J = 8.8Hz,2H), 7.48 (d, J = 8.8 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 7.10 (d, J = 8.2 Hz, 2H), 6.99 (d, J = 8.6 Hz,2H), 6.74 (s, 1H), 4.34 (q, J = 7.1 Hz, 2H), 4.07 (t, J = 7.4 Hz, 2H), 2.38 (s, 3H), 2.28–2.12(m,4H), 1.99 (dq, J = 13.9, 7.5 Hz, 1H), 1.42–1.33 (m, 12H).19F NMR (377 MHz, CDCl3) δ – 62.5.13C NMR (126 MHz, CDCl3) δ 166.5, 158.9, 150.7, 145.5, 144.4 (q, J = 38.8 Hz), 143.1,140.0,139.6, 131.0, 130.0, 129.0, 128.9, 126.0, 125.1, 124.7, 121.2 (q, J = 269.0 Hz), 120.5, 106.7, 85.1, 60.8, 45.3, 37.5, 33.8, 33.7, 28.1, 21.5, 14.5. HRMS-ESI+(m / z): [M+1]+calcd. for C35H38F3N4O6S+, 699.2459; found, 699.2442. (R)-5-(1-(3,5-Bis(trifluoromethyl)phenyl)-2-methylaziridin-2-yl)-2-methylcyclohex-2-en-1-one(12i). Prepared from 5z (0.150 mmol), purified on neutral alumina column (0% to 10%EtOAc inhexanes), and obtained as a colorless oil (8.0 mg, 14%). 1H NMR (400 MHz, CDCl3)δ 7.46 (s,1H), 7.20 (s, 2H), 6.79 (s, 1H), 2.74–2.60 (m, 1H), 2.59–2.26 (m, 4H), 2.16 (m, 1H),2.00–1.92(m, 1H), 1.80 (s, 3H), 1.02 (s, 3H). 19F NMR (376 MHz, CDCl3) δ –63.0. 13C NMR (126 MHz,CDCl3) δ 199.0, 198.9, 152.0, 151.9, 144.1, 143.8, 136.1, 135.9, 132.5 (q, J = 36.5Hz), 120.6,120.1 (q, J = 272.8 Hz), 115.6, 45.2, 45.0, 42.5, 42.2, 40.9, 40.6, 39.0, 38.5, 28.7,28.4, 16.4,16.0, 15.9. (Excess 13C NMR resonances are attributed to an inseparable mixture ofdiastereomers). HRMS-ESI+ (m / z): [M+1]+ calcd. for C18H18F6NO+, 378.1287; found,378.1279.Methyl 2-(5-methoxy-1-(4-((3S,6aR,6bS,9aS,11aS,11bR)-3-methoxy-9a,11b-dimethyl-9- oxohexadecahydro-5H-cyclopenta[1,2]phenanthro[8a,9-b]azirin-5-yl)benzoyl)-2-methyl-1H- indol-3-yl)acetate (12j). Prepared from 5y (0.100 mmol), purified on deactivated silica gelcolumn (10% to 25% EtOAc in hexanes), and obtained as a yellow solid (14.9 mg, 23%).1HNMR(400 MHz, CDCl3) δ 7.63 (d, J = 8.5 Hz, 2H), 7.01–6.86 (m, 4H), 6.65 (dd, J = 9.0, 2.6 Hz,1H),3.84 (s, 3H), 3.70 (s, 3H), 3.68 (s, 2H), 3.39 (dt, J = 10.5, 5.3 Hz, 1H), 3.22 (s, 3H), 2.53–2.41 (m, 2H), 2.40 (s, 3H), 2.37–2.29 (m, 1H), 2.16–1.94 (m, 2H), 1.83 (dt, J = 13.6, 5.7 Hz, 5H), 1.66–1.31(m, 6H), 1.29–1.20 (m, 2H), 1.18 (s, 3H), 0.87 (s, 3H), 0.82 (dd, J = 11.5, 4.0 Hz, 1H),0.72 (dd, J =13.3, 5.7 Hz, 1H).13C NMR (126 MHz, CDCl3) δ 220.8, 171.7, 169.2, 155.9, 155.6,136.3, 131.7, 131.4, 130.4, 128.3, 120.2, 115.0, 111.6, 111.5, 101.2, 77.4, 55.9, 52.2, 51.9, 49.9, 49.3, 47.7, 47.1,36.1, 36.0, 35.8, 34.8, 31.8, 31.3, 30.5, 30.4, 26.6, 21.9, 21.8, 21.1, 13.9, 13.2.HRMS-ESI+ (m / z):[M+1]+calcd. for C40H49N2O6+, 653.3585; found, 653.3576. EXAMPLE 8 B.5 Depyridylation of Pyridinium Aziridines A 20-mL 10.0 equiv.) andammonium chloride (107 mg, 2.00 mmol, 10.0 equiv.) was heated under vacuum at 65 ℃ for30min, which was then taken to an N2filled dry box. Tetrahydrofuran (0.5 mL) was added, followedby a solution of I2in tetrahydrofuran (0.10 M, 0.10 mL, 5.0 mol%). The mixture wasvigorouslystirred until the color of the liquid phase disappeared. Pyridinium aziridine (5, 0.200 mmol, 1.00 equiv.) was dissolved in tetrahydrofuran (0.5 mL), and added to the suspension, which was then stirred for 12 h at 23 ℃. The mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The crude mixture was purified as indicated below to afford the indicated compounds. Compound structures are shown in FIG.39. 3-Azatricyclo[3.2.1.02,4]octane (13a). Prepared from 5e. NMR analysis of the reaction mixture at 4 h indicated quantitative conversion. Without further purification, 13a was transformed to 14 and 15 for isolation. (E)-5-(3,3-Dimethylaziridin-2-yl)-3-methylpent-2-en-1-yl acetate (13b). Prepared from 5v, purified on silica gel flash chromatography (hexanes / acetone = 4:1 to 1:1, with 0.1% Et3N), andobtained as a yellow oil (23.2 mg, 55%). 1H NMR (400 MHz, CDCl3) δ 5.37 (td, J = 7.1, 1.3Hz,1H), 4.58 (d, J = 7.1 Hz, 2H), 2.26–2.15 (m, 1H), 2.19–2.08 (m, 1H), 2.04 (s, 3H), 1.93 (t, J = 6.7Hz, 1H), 1.72 (s, 3H), 1.68–1.54 (m, 2H), 1.31 (s, 3H), 1.22 (s, 3H). HRMS-ESI+(m / z):[M+1]+calcd. for C12H22NO2+, 212.1645; found, 212.1637. These spectral data are well-matched tothose reported in the literature

[0106] . (1R,10S)-4,12,12-Trimethyl-9-methylene-5-azatricyclo[8.2.0.04,6]dodecane (13c). Prepared from5x, purified on silica gel flash chromatography (hexanes / acetone = 4:1 to 1:1, with 0.1%Et3N),and obtained as a colorless oil (18.7 mg, 43%). 1H NMR (400 MHz, CDCl3) δ 4.95 (d, J= 1.7 Hz,1H), 4.82 (d, J = 1.7 Hz, 1H), 2.59 (q, J = 9.3 Hz, 1H), 2.40–2.28 (m, 1H), 2.23–2.09 (m, 2H), 2.00 (ddd, J = 13.1, 8.7, 4.6 Hz, 1H), 1.90 (dd, J = 11.0, 4.2 Hz, 1H), 1.73 (t, J = 9.6 Hz, 1H), 1.69– 1.60 (m, 2H), 1.56–1.52 (m, 1H), 1.51–1.45 (m, 1H), 1.21–1.15 (m, 1H), 1.08 (s, 3H), 0.98 (s, 3H),0.95 (s, 3H), 0.64 (td, J = 12.9, 4.8 Hz, 1H). HRMS-ESI+(m / z): [M+1]+calcd. ForC15H26N+,220.2060; found, 220.2059. These spectral data are well-matched to thosereported in theliterature

[0106] . N-Tosyl-3- . of 13a was filtered through celite to a 20-mL scintillation vial containing p-methylbenzenesulfonyl chloride (57.2 mg, 0.300 mmol, 1.50 equiv.), N,N-dimethylpyridin-4-amine (1.2 mg, 0.0010 mmol, 5.0 mol%), and potassium carbonate (55.3 mg, 0.400 mmol, 2.00 equiv.). The mixture was stirred at 23 ℃ for 12 h, and filtered through celite. The filtrate was concentrated under reduced pressure, and the crude mixture was purified by silica gel flash chromatography (10% EtOAc in hexanes). 14was obtained as a white solid (35.0 mg, 67%).1H NMR (400 MHz,CDCl3) δ 7.79 (d, J = 6.6Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 2.90 (s, 2H), 2.43 (s, 5H), 1.56–1.39 (m, 3H), 1.29–1.17 (m, 2H),0.74 (d, J = 10.1 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 144.2, 136.0,129.7, 127.7, 42.0, 35.9,28.3, 25.7, 21.7. These spectral data are well-matched to those reported in the literature

[0107] . tert-Butyl 3- reaction mixture of 13a was filtered to a 50-mL round bottom flask, and the filtrate was concentrated under reduce pressure. To the resulting yellow oil was added dichloromethane (1.0 mL), triethylamine (50.6 mg, 0.500 mmol, 2.50 equiv.), and the mixture was cooled to 0 ℃. A solution of di-tert- butyl dicarbonate (87.3 mg, 0.400 mmol, 2.00 equiv.) in dichloromethane (1.0 mL) was added. The reaction was stirred for 12 h and allowed to warm to 23 ℃. The reaction mixture was concentrated under reduced pressure, and the crude mixture was filtered through a silica gel plug (17% EtOAc in hexanes). The filtrate was concentrated and dried under vacuum to afford 15as a pale yellow solid (36.8 mg, 88%).1H NMR (400 MHz,CDCl3) δ 2.50 (s, 2H), 2.46 (s, 2H),1.47–1.39 (m, 11H), 1.39–1.29 (m, 1H), 1.23–1.12 (m, 2H), 0.75 (d, J = 10.0 Hz, 1H). 13C NMR(101 MHz, CDCl3) δ 161.5, 80.7, 39.1, 36.0, 28.1, 28.1, 26.0. HRMS-ESI+(m / z): [M+Na]+calcd.for C12H19NO2Na+, 232.1308; found, 232.1304. Thesespectral data are well-matched to thosereported in the literature

[0108] . EXAMPLE 9 B.6 Synthesis of Iodosylbenzene Derivatives A 2-dram vial was 0.500 mmol, 1.00 equiv.), NaOH (600 mg, 15.0 mmol, 30.0 equiv.), and water (5.0 mL) at 23 ℃. The vial was capped and shaken vigorously for 5 min. The resulting solid was isolated by filtration, washed with ether (2 × 1.5 mL) and water (6 × 1.5 mL), dried in vacuo, and stored in the dark at 9 ℃. Various compounds are shown in FIG.40. 1-Bromo-4-iodosylbenzene (S6a). Prepared from (4-bromophenyl)-λ3-iodanediyl diacetate (S5a,149 mg) and obtained as a pale-yellow solid (120 mg, 80% yield).1H NMR (δ, 23 ℃,400 MHz,CD3OD): 7.94 (d, J = 8.2 Hz, 2H), 7.73 (d, J = 8.7 Hz, 2H). The spectroscopic data isin goodagreement with that reported in the literature

[0109] . 4-Iodosylbenzonitrile (S6b). Prepared from (4-cyanophenyl)-λ3-iodanediyl diacetate (S5b, 174 mg) and obtained as a pale-yellow solid (111 mg, 91% yield).1H NMR (δ, 23 ℃, 400 MHz, CD3OD): 8.19 (d, J = 8.7 Hz, 2H), 7.93 (d, J = 8.8 Hz, 2H). The spectroscopic data is in good agreement with that reported in the literature

[0109] . 1-Iodosyl-4-nitrobenzene (S6c). Prepared from (4-cyanophenyl)-λ3-iodanediyl diacetate (S5c, 184mg) and obtained as an orange solid (110 mg, 83% yield).1H NMR (δ, 23 ℃, 400MHz, CD3OD):8.40 (d, J = 9.2 Hz, 2H), 8.26 (d, J = 9.1 Hz, 2H). The spectroscopic data is ingood agreementwith that reported in the literature

[0110] . EXAMPLE 10 C. Reaction Optimization Studies C.1 Optimization of Aliphatic Olefin Aziridination Table 4. Evaluation of Ag(I)-catalyzed intermolecular aziridination. Yields were determined by1H NMR analysis of the crude mixture with 1,3,5-trimethoxybenzene as the internal Entry Catalyst Ligand NMR yield 1 AgOTf TPA 29% 2 AgOTf Tp*Br 26% 3 AgOTf Tp 13% 4* AgOTf tBu3terpy 62% 5* CuI phen 12% 6* Cu(tBu2bpy)(OTf)2 33% 7* Rh2(tfacam)2(5 mol%) 50% 8* Mn(TPP)Cl 5% * Carried out in CH3CN. Table 5. Evaluation of the impact of reaction stoichiometry on metal-free aziridination. Yields were determined by1H NMR analysis of the crude mixture with 1,3,5- trimethoxybenzene as the internal standard. Entry Cyclohexene py–NH2 PhI=O NMR yield1 1.0 equiv. 1.0 equiv. 1.0 equiv. 33%2 1.0 equiv. 1.0 equiv. 2.0 equiv. 46%3 1.0 equiv. 1.2 equiv. 2.4 equiv. 34%4 1.0 equiv. 1.6 equiv. 3.0 equiv. 20%5 5.0 equiv. 1.0 equiv. 2.0 equiv. 70%6 5.0 equiv. 1.0 equiv. 3.0 equiv. 67%7 3.0 equiv. 1.0 equiv. 2.0 equiv. 68%

[0009] Table 6. Evaluation of the impact of CH3CN / HFIP ratio on olefin aziridination. Yieldsweredetermined by1H NMR analysis of the crude mixture with 1,3,5-trimethoxybenzene as the internal standard. 1 100% 71% 5 15% 63% 6 2.0 equiv 68% * Using 1.0 equiv. of cyclohexene (2a). EXAMPLE 11 C.2 Problematic Olefin Substrates Olefin substrates with free OH, free NH, 1,3-dienes, or allyl esters suffer from low yields or decomposition during aziridination. Non-limiting problematic compounds are found in FIG.41. EXAMPLE 12 A.^General Considerations A.1 Materials All chemicals and solvents were obtained as ACS reagent grade and used as received. Styrene was acquired from BeanTown Chemical (BTC).4-Fluorostyrene (104d) and 2- bromostyrene (104f) were purchased from Matrix Scientific. 4-Trifluoromethylstyrene (104g), ibuprofen, 4-(dipropylsulfamoyl)benzoic acid (Probenecid,), and triethyl amine were acquired from Oakwood. Hexanes, ethyl acetate, dichloromethane, tetrabutylammonium iodide, 4- vinylpyridine (104k) and 1,1-diphenylethane (104m) were obtained from Sigma Aldrich. 2-((3- Chloro-2-methylphenyl)amino)benzoic acid (Tufnil), 2-(1-(4-chlorobenzoyl)-5-methoxy-2- methyl-1H-indol-3-yl)acetic acid (Indometacin) and tris(2-phenylpyridine)iridium were acquired from Ambeed.4-Vinylbenzoic acid, and lithium bromide were acquired from TCI.3-Nitrostyrene (104j) and α-methyl styrene (104l) were acquired from Acros. Anhydrous sodium sulfate and anhydrous potassium carbonate were obtained from VWR. Acetonitrile and methanol were obtained from Fischer Scientific. Dry dichloromethane (purchased from Fisher scientific, HPLC grade) was obtained from a drying column and stored over activated 4 Å molecular sieves

[0111] . NMR solvents were purchased from Cambridge Isotope Laboratories and were used as received. All reactions were carried out under ambient atmosphere unless otherwise noted. Pyridinium aziridines 102a, 102p-102z, 102ab-102ad, and 106 were prepared according to literature methods

[0065] . A.2 Characterization Details1H and13C NMR spectral acquisitions were recorded on an AvanceNeo 500 or a AcsendTM400 NMR and were referenced against residual proteo solvent signals:CDCl3 (7.26 ppm,1H; 77.16 ppm,13C) and acetonitrile-d3(1.94 ppm,1H)

[0112] .1H NMR data are reported as follows: chemical shift (δ, ppm), (multiplicity: s (singlet), d (doublet), t (triplet), m (multiplet), br (broad), integration).13C NMR data are reported as follows: chemical shift (δ, ppm). Mass spectrometry data were recorded on either Orbitrap FusionTMTribridTMMass Spectrometeror Q ExactiveTMFocus Hybrid Quadrupole-OrbitrapTMMass Spectrometer from ThermoFisher Scientific. Fluoresence spectra and Stern-Volmer analyses were conducted using a Ocean SR miniature spectrophotometer. A.3. X-Ray Diffraction Details Experimental details regarding sample crystallization are included in the synthetic procedures for the relevant compounds. A Bruker APEX 2 Duo X-ray (three-circle) diffractometer was used for crystal screening, unit cell determination, and data collection for the X-ray crystal structures of 105v and 108. Crystal suitable for X-ray diffraction were mounted on a MiTeGen dual-thickness micro-mount and placed under a cold N2stream (Oxford). The X-ray radiation employed was generated from a Mo sealed X-ray tube (Kα= 0.70173 Å with a potential of 40 kV and a current of 40 mA). Bruker AXS APEX II software was used for data collection and reduction. Absorption corrections were applied using the 4 program SADABS. A solution was obtained using XT / XS in APEX2 and refined in Olex2 [113-115]. Hydrogen atoms were placed in idealized positions and were set riding on the respective parent atoms. All non- hydrogen atoms were refined with anisotropic thermal parameters. The structure was refined (weighted least squares refinement on F2) to convergence

[0115] . ^ EXAMPLE 13 B. Synthesis and Characterization B.1 Synthesis of N-pyridinium Aziridine 2aa

[0010] Under an N2atmosphere, a 100-mL round-bottom flask was charged with 1-amino-2,4,6- triphenylpyridin-1-ium tetrafluoroborate (213 mg, 0.520 mmol, 1.00 equiv) tetrabutylammonium iodide (9.6 mg, 0.026 mmol, 5.0 mol%), 4 Å molecular sieves, iodosylbenzene (116 mg, 0.520 mmol, 1.00 equiv), and 4-vinylbenzyl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3- yl)acetate (250 mg, 0.520 mmol, 1.00 equiv). Acetonitrile (4 mL) was added to the reaction mixture, which was then stirred at 23 ^C for 12 h. Under an ambient atmosphere, the reaction mixture was filtered through a pad of Celite and concentrated in vacuo. The residue was purified by silica gel flash chromatography (1:1 ethyl acetate:hexanes) to afford the compound 102aa as off white solid (254 mg, 44% yield).1H NMR (400 MHz, CD3CN) δ 8.18 (s, 2H), 8.11 – 8.00 (m, 2H), 8.01–7.79 (m, 5H), 7.75–7.61 (m, 3H), 7.57 (d, J = 8.6 Hz, 2H), 7.48 (d, J = 33.5 Hz, 7H), 7.17–6.83 (m, 4H), 6.66–6.48 (m, 3H), 5.08 (s, 2H), 3.81 (s, 3H), 3.47 (dd, J = 8.3, 5.7 Hz, 1H), 2.68 (dd, J = 8.4, 3.1 Hz, 1H), 2.40 (dd, J = 5.8, 3.1 Hz, 1H), 2.31 (s, 2H), 2.18 (s, 3H).13C NMR (101 MHz, CD3CN) δ 171.2, 168.9, 156.7, 153.9, 153.8, 139.1, 137.3, 136.6, 135.0, 134.6, 134.3, 132.6, 132.2, 132.2, 131.8, 131.4, 131.4, 130.5, 130.3, 129.7, 129.7, 129.4, 128.8, 128.0, 126.8, 126.2, 115.7, 113.4, 112.1, 102.0, 66.4, 60.6, 55.9, 54.0, 30.3, 14.2, 13.4. HRMS-ESI: calculated for [M+] = 794.2780, observed [M+] = 794.2764. B.2 Synthesis of N-pyridinium Aziridine 108 A 100-mL Schlenk was mg, 1.00 equiv), which was washed with pentane. Dry THF (6.0 mL) was added to the reaction vessel and the reaction mixture was cooled to 0 ^C.1-Amino-2,4,6-triphenylpyridin-1-ium tetrafluoroborate (943 mg, 2.30 mmol, 1.00 equiv) was added to the reaction as a solid and the reaction mixture was stirred at 0 ^C for 15 min. A THF solution (6.0 mL) of diphenyl(vinyl)sulfonium trifluoromethanesulfonate

[0116] (1.00 g, 2.76 mmol, 1.20 equiv) was added dropwise. The reaction mixture was allowed to warm to 23 ^C at which temperature it was stirred for 12 h. Solids were removed from the reaction mixture by filtration and were washed with EtOAc. The combined filtrate was concentrated under reduced pressure and the residue was purified using silica gel column chromatography with 50% EtOAc:Hexane solution. The product (108) was obtained as white solid (274 mg, 55% yield).1H NMR (400 MHz, CD3CN): δ 8.17 (s, 2H), 8.02 (m, 6H), 7.74 (dd, J = 5.2, 1.9 Hz, 6H), 7.69–7.60 (m, 3H), 2.27–2.11 (m, 4H).13C NMR (101 MHz, CD3CN) δ 154.2, 153.9, 134.9, 132.8, 132.7, 132.5, 130.7, 130.5, 130.1, 129.0, 127.0, 41.0.19F NMR (376 MHz, CD3CN): –79.3. HRMS-ESI: calculated for [M+] = 349.1699, observed [M+] = 349.1699. EXAMPLE 14 C. Photocatalytic Olefin Hydroaziridination C.1 General Procedure for Olefin Hydroxyaziridination A 40-mL was (51.0 mg, 0.100 mmol, 1.00 equiv), Ir(ppy)3(0.7 mg, 0.001 mmol, 1 mol%), and LiBr (8.70 mg, 0.100 mmol, 1.00 equiv). The solid compounds were dissolved in a 1:1 mixture of MeCN:H2O (2 mL total). Triethylamine (28.0 µL, 0.200 mmol, 2.00 equiv) and the appropriate styrene derivative (104, 0.150 mmol, 1.50 equiv) were added. The reaction mixture was purged with oxygen. With stirring, the reaction was irradiated with blue LED lights for 12 h; the temperature was maintained at 23 ℃ using air cooling provided by a fan. The reaction mixture was diluted with distilled water (5 mL) and extracted with ethyl acetate (3 × 5 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography (using a Hexane:EtOAc gradient, 4:1 ^ 1:100) to afford the corresponding hydroxyaziridination product 105. Various examples of products are found in FIG. 48. 1-Phenyl-2-(2-phenylaziridin-1-yl)ethan-1-ol (105a) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a pale-yellow liquid (15.5 mg, 65% yield).1H NMR (400 MHz, CDCl3) δ 7.53– 7.16 (m, 10H), 4.91 (dd, J = 9.0, 3.5 Hz, 1H), 3.36 (br, 1H), 2.88 (dd, J = 12.0, 8.9 Hz, 1H), 2.66– 2.31 (m, 2H), 1.96 (d, J = 3.5 Hz, 1H), 1.78 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3) δ 7.60–7.11 (m, 10H), 4.88 (dd, J = 9.1, 3.4 Hz, 1H), 3.36 (br, 1H), 2.95 (dd, J = 12.0, 9.1 Hz, 1H), 2.71–2.19 (m, 2H), 2.00 (d, J = 3.4 Hz, 1H), 1.84 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 141.7, 139.6, 128.3, 128.2, 127.5, 127.0, 126.0, 125.9, 72.9, 68.5, 41.2, 37.4.13C NMR (101 MHz, CDCl3) δ 141.7, 139.7, 128.3, 127.6, 127.0, 126.0, 125.9, 73.1, 68.5, 41.1, 38.0. HRMS- ESI+: calculated for [M+H+] = 240.1383, observed [M+H+] = 240.1378. 2-(2-Phenylaziridin-1-yl)-1-(p-tolyl)ethan-1-ol (105b) Prepared from 4-methylstyrene (104b, 20.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a pale-yellow liquid (14.6 mg, 58% yield).1H NMR (400 MHz, CDCl3): δ 7.30 (dd, J = 7.1, 1.2 Hz, 2H), 7.28–7.19 (m, 5H), 7.13 (d, J = 7.9 Hz, 2H), 4.87 (dd, J = 9.2, 3.4 Hz, 1H), 3.30 (br, 1H), 2.87 (dd, J = 11.9, 9.1 Hz, 1H), 2.50 (dd, J = 6.6, 3.4 Hz, 1H), 2.47–2.41 (m, 1H), 2.33 (s, 3H), 1.94 (d, J = 3.4 Hz, 1H), 1.77 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.38–7.27 (m, 2H), 7.28–7.19 (m, 5H), 7.13 (d, J = 7.9 Hz, 2H), 4.87 (dd, J = 9.1, 3.5 Hz, 1H), 3.29 (br, 1H), 2.87 (dd, J = 11.9, 9.1 Hz, 1H), 2.50 (dd, J = 6.6, 3.5 Hz, 1H), 2.45 (dd, J = 12.0, 3.3 Hz, 1H), 2.34 (s, 3H), 1.94 (d, J = 3.4 Hz, 1H), 1.77 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 139.7, 138.7, 137.3, 129.0, 128.3, 127.0, 126.0, 125.9, 73.0, 68.6, 41.1, 38.0, 21.1.13C NMR (101 MHz, CDCl3): δ 139.7, 138.8, 137.2, 129.0, 128.2, 127.0, 126.1, 125.8, 72.8, 68.6, 41.2, 37.4, 21.1. HRMS-ESI+: calculated for [M+H+] = 254.1539, observed [M+H+] = 254.1531. 1-(4-Methoxyphenyl)-2-(2-phenylaziridin-1-yl)ethan-1-ol (105c) Prepared from 4- methoxystyrene (104c, 20.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin- 1-yl)pyridine-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a pale-yellow liquid (13.2 mg, 49% yield).1H NMR (400 MHz, CDCl3) δ 7.42–7.08 (m, 14H), 6.94–6.56 (m, 4H), 4.76 (m, 2H), 3.72 (s, 6H), 2.83 (m, 2H), 2.67–2.18 (m, 4H), 1.89 (dt, J=24.2, 3.1 Hz, 2H), 1.81–1.56 (m, 2H).13C NMR (101 MHz, CDCl3): δ 159.1, 159.0, 139.8, 139.7, 134.0, 133.9, 128.3, 128.2, 127.2, 127.1, 127.0, 126.1, 126.0, 113.9, 113.7, 72.8, 72.5, 68.6, 68.5, 55.2, 41.2, 41.2, 38.0, 37.4. HRMS-ESI+: calculated for [M+H+] = 270.1489, observed [M+H+] = 270.1484. 1-(4-Fluorophenyl)-2-(2-phenylaziridin-1-yl)ethan-1-ol (105d) Prepared from 4-fluorostyrene (104d, 18.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1- ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.4 mg, 64% yield).1H NMR (400 MHz, CDCl3): δ 7.31 (m, 4H), 7.28–7.18 (m, 3H), 6.99 (t, J = 8.7 Hz, 2H), 4.88 (dd, J = 8.8, 3.6 Hz, 1H), 3.41 (br, 1H), 2.84 (dd, J = 11.9, 8.8 Hz, 1H), 2.62–2.30 (m, 2H), 1.95 (d, J = 3.4 Hz, 1H), 1.77 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3): 7.38–7.28 (m, 4H), 7.25–7.22 (m, 3H), 7.01 (t, J = 8.7 Hz, 2H), 4.85 (dd, J = 9.1, 3.5 Hz, 1H), 3.34 (br, 1H), 2.93 (dd, J = 12.0, 9.0 Hz, 1H), 2.42 (dd, J = 6.6, 3.4 Hz, 1H), 2.36 (dd, J = 12.0, 3.6 Hz, 1H), 2.00 (d, J = 3.4 Hz, 1H), 1.84 (d, J = 6.5 Hz, 1H).13C NMR (125 MHz, CDCl3): δ 162.2 (d, J = 245.0 Hz), 139.5, 137.5, 128.3, 127.5 (d, J = 8.7 Hz) , 127.1, 126.0, 115.1 (d, J = 20.0 Hz), 72.2, 68.4, 41.2, 37.4.13C NMR (101 MHz, CDCl3): δ 162.2 (d, J = 195.0 Hz), 139.6, 137.5 (d, J = 3.0 Hz), 128.3, 127.6 (d, J = 7.0 Hz), 127.1, 126.0, 115.1 (d, J = 17.0 Hz), 72.5, 68.5, 41.2, 38.0. HRMS-ESI+: calculated for [M+H+] = 258.1289, observed [M+H+] = 258.1279. 1-(4-Chlorophenyl)-2-(2-phenylaziridin-1-yl)ethan-1-ol (105e) Prepared from 4-chlorostyrene (104e, 19.0 µL, 0.150 mmol, 1.50 equiv,) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1- ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (20.2 mg, 74% yield).1H NMR (400 MHz, CDCl3): δ 7.40– 7.28 (m, 2H), 7.28–7.22 (m, 5H), 7.22–7.15 (m, 2H), 4.87 (dd, J = 8.7, 3.6 Hz, 1H), 3.41 (br, 1H), 2.81 (dd, J = 11.9, 8.7 Hz, 1H), 2.50 (dd, J = 11.9, 3.6 Hz, 1H), 2.45 (dd, J = 6.6, 3.5 Hz, 1H), 1.96 (d, J = 3.4 Hz, 1H), 1.77 (d, J = 6.6 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.34–7.19 (m, 9H), 4.85 (dd, J = 8.9, 3.6 Hz, 1H), 2.91 (dd, J = 12.0, 8.9 Hz, 1H), 2.44–2.33 (m, 2H), 2.00 (d, J = 3.4 Hz, 1H), 1.83 (d, J = 6.5 Hz, 1H).13CNMR (101 MHz, CDCl3): δ 140.3, 139.4, 133.2, 128.4, 128.3, 127.3, 127.1, 126.0, 72.2, 68.3, 41.3, 37.4.13C NMR (101 MHz, CDCl3): δ 140.2, 139.5, 133.2, 128.4, 128.3, 127.3, 127.1, 125.9, 72.4, 68.3, 41.2, 38.0. HRMS-ESI+: calculated for [M+H+] = 274.0993, observed [M+] = 274.0987. 1-(2-Bromophenyl)-2-(2-phenylaziridin-1-yl)ethan-1-ol (105f) Prepared from 2-bromostyrene (104f, 19.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1- ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (17.8 mg, 56% yield).1H NMR (400 MHz, CDCl3): δ 7.54 (m, 2H), 7.41 (dd, J = 7.9, 1.2 Hz, 2H), 7.31–7.01 (m, 14H), 5.13 (td, J = 8.8, 2.9 Hz, 2H), 2.73 (m, 2H), 2.51 (dt, J = 8.8, 2.7 Hz, 2H), 2.45–2.30 (m, 2H), 1.91 (dd, J = 8.7, 3.4 Hz, 2H), 1.82 (d, J = 6.5 Hz, 1H), 1.72 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 140.5, 140.4, 139.7, 139.5, 132.4, 132.4, 128.9, 128.8, 128.3, 128.2, 127.8, 127.7, 127.6, 127.1, 127.0, 126.1, 126.0, 121.6, 121.4, 72.0, 71.6, 66.4, 66.1, 41.4, 40.9, 38.0, 37.2. HRMS-ESI+: calculated for [M+H+] = 318.0488, observed [M+H+] = 318.0482. 2-(2-Phenylaziridin-1-yl)-1-(4-(trifluoromethyl)phenyl)ethan-1-ol (105g) Prepared from 1- (trifluoromethyl)-4-vinylbenzene (104g, 22.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1- (2-phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (19.6 mg, 64% yield).1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 8.1 Hz, 2H), 7.45 (d, J = 8.1 Hz, 2H), 7.35–7.22 (m, 3H), 7.23–6.92 (m, 2H), 4.95 (dd, J = 8.4, 3.6 Hz, 1H), 3.51 (br, 1H), 2.79 (dd, J = 11.9, 8.3 Hz, 1H), 2.61 (dd, J = 12.0, 3.6 Hz, 1H), 2.40 (dd, J = 6.5, 3.5 Hz, 1H), 1.97 (d, J = 3.5 Hz, 1H), 1.80 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 8.1 Hz, 2H), 7.49 (d, J = 8.1 Hz, 2H), 7.39–7.26 (m, 2H), 7.25–7.09 (m, 3H), 4.93 (dd, J = 8.8, 3.7 Hz, 1H), 3.45 (br, 1H), 2.93 (dd, J = 12.0, 8.9 Hz, 1H), 2.48–2.33 (m, 2H), 2.00 (d, J = 3.4 Hz, 1H), 1.83 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 145.9, 139.3, 135.9, 129.8 (q, J = 33.0 Hz), 128.3, 127.2 (q, J = 270.0 Hz), 126.2, 126.0, 125.2 (q, J = 4.0 Hz), 72.2, 68.2, 41.5, 37.3.13C NMR (101 MHz, CDCl3) δ 145.7, 139.4, 129.9 (q, J = 32.8 Hz),, 128.3, 127.1 (q, J = 272.0 Hz), 126.2, 125.4 (q, J = 3.8 Hz), 72.5, 68.2, 41.3, 38.0. HRMS-ESI+: calculated for [M+H+] = 308.1257, observed [M+H+] = 308.1250. 4-(1-Hydroxy-2-(2-phenylaziridin-1-yl)ethyl)benzonitrile (105h) Prepared from 1- (trifluoromethyl)-4-vinylbenzene (104h, 19.0 mg, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1- (2-phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.6 mg, 63% yield).1H NMR (400 MHz, CDCl3): δ 7.49 (dd, J = 8.3, 1.8 Hz, 2H), 7.45–7.31 (m, 2H), 7.29–7.12 (m, 3H), 7.13–6.96 (m, 2H), 4.86 (dd, J = 8.2, 3.7 Hz, 1H), 3.52 (br, 1H), 2.68 (dd, J = 11.6, 8.5 Hz, 1H), 2.55 (dd, J = 11.9, 2.6 Hz, 1H), 2.31 (dd, J = 6.7, 3.4 Hz, 1H), 2.05–1.83 (m, 1H), 1.72 (dd, J = 6.6, 1.6 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 8.4 Hz, 2H), 7.54–7.46 (m, 2H), 7.35– 7.27 (m, 3H), 7.27–7.16 (m, 2H), 4.92 (dd, J = 8.7, 3.8 Hz, 1H), 3.53 (br, 1H), 2.90 (dd, J = 12.0, 8.7 Hz, 1H), 2.57–2.22 (m, 2H), 1.99 (d, J = 3.4 Hz, 1H), 1.82 (d, J = 6.6 Hz, 1H).13C NMR (100 MHz, CDCl3): δ 147.1, 139.3, 132.1, 128.4, 127.2, 126.6, 125.9, 118.8, 111.3, 72.4, 67.9, 41.3, 38.0.13C NMR (100 MHz, CDCl3): δ 147.1, 139.3, 132.1, 128.4, 127.2, 126.6, 125.9, 118.8, 111.3, 72.4, 67.9, 41.3, 38.0. HRMS-ESI+: calculated for [M+H+] = 265.1335, observed [M+H+] = 265.1331. Ethyl 4-(1-hydroxy-2-(2-phenylaziridin-1-yl)ethyl)benzoate (105i) Prepared from ethyl 4- vinylbenzoate (104i, 26.0 mg, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin- 1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (17.4 mg, 56% yield).1H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.3 Hz, 2H), 7.34–7.21 (m, 3H), 7.20–7.11 (m, 2H), 4.95 (dd, J = 8.7, 3.6 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3.48 (br, 1H), 2.83 (dd, J = 11.9, 8.6 Hz, 1H), 2.54 (dd, J = 11.9, 3.6 Hz, 1H), 2.45 (dd, J = 6.6, 3.5 Hz, 1H), 1.96 (d, J = 3.4 Hz, 1H), 1.79 (d, J = 6.6 Hz, 1H), 1.39 (t, J = 7.1 Hz, 3H).1H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 8.4 Hz, 1H), 7.65–7.37 (m, 1H), 7.37–6.88 (m, 7H), 4.93 (dd, J = 8.9, 3.4 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3.47 (br, s), 2.90 (dd, J = 11.9, 8.9 Hz, 1H), 2.46 (dt, J = 9.7, 3.5 Hz, 2H), 1.99 (d, J = 3.3 Hz, 1H), 1.82 (d, J = 6.6 Hz, 1H), 1.39 (t, J = 7.2 Hz, 3H).13C NMR (100 MHz, CDCl3): δ 166.4, 146.8, 139.4, 129.7, 129.6, 128.3, 127.1, 126.0, 125.8, 72.4, 68.2, 60.9, 41.4, 37.4, 14.3.13C NMR (100 MHz, CDCl3): δ 166.4, 146.8, 139.5, 129.7, 129.6, 128.3, 127.1, 125.9, 125.8, 72.7, 68.2, 60.9, 41.1, 38.1, 14.3. HRMS-ESI+: calculated for [M+H+] = 312.1594, observed [M+H+] = 312.1582. 1-(3-Nitrophenyl)-2-(2-phenylaziridin-1-yl)ethan-1-ol (105j) Prepared from 1-nitro-4- vinylbenzene (104j, 19.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1- yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (23.0 mg, 81% yield).1H NMR (400 MHz, CDCl3): δ 8.24–8.10 (m, 2H), 8.01 (dd, J = 7.3, 2.3 Hz, 2H), 7.61 (dd, J = 21.3, 7.7 Hz, 2H), 7.39 (dt, J = 12.5, 7.9 Hz, 2H), 7.32–7.02 (m, 10H), 4.90 (td, J = 7.7, 3.7 Hz, 2H), 2.87 (dd, J = 12.0, 8.6 Hz, 1H), 2.71 (dd, J = 12.0, 7.9 Hz, 1H), 2.59 (dd, J = 12.0, 3.8 Hz, 1H), 2.50–2.26 (m, 3H), 1.91 (dd, J = 9.8, 3.4 Hz, 2H), 1.74 (dd, J = 9.7, 6.6 Hz, 2H).13C NMR (126 MHz, CDCl3): δ 148.2, 148.1, 144.1, 144.0, 139.2, 139.1, 132.1, 131.9, 129.2, 129.1, 128.3, 128.3, 127.2, 127.2, 125.9, 125.9, 122.5, 122.4, 121.1, 121.0, 72.1, 71.7, 68.0, 67.9, 41.6, 41.3, 37.9, 37.2. HRMS- ESI+: calculated for [M+H+] = 285.1234, observed [M+H+] = 285.1228. 2-(2-Phenylaziridin-1-yl)-1-(pyridin-2-yl)ethan-1-ol (105k) Prepared from 4-vinylpyridine (104k, 16.0 µL, 0.150 mmol, 1.50 equiv.) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1- ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (10.0 mg, 40% yield).1H NMR (400 MHz, CDCl3):1H NMR (400 MHz, CD3CN): δ 8.50–8.27 (m, 4H), 7.41–7.13 (m, 9H), 4.85–4.80 (m, 5H), 3.83 (br, 2H), 2.75 (dd, J = 12.1, 7.4 Hz, 1H), 2.66 (d, J = 4.0 Hz, 2H), 2.57 (dd, J = 12.1, 4.8 Hz, 1H), 2.48 (dd, J = 6.5, 3.4 Hz, 1H), 2.44 (dd, J = 6.5, 3.4 Hz, 1H), 1.86 (d, J = 3.4 Hz, 1H), 1.82–1.73 (m, 3H).13C NMR (101 MHz, CDCN3): δ 152.9, 152.8, 150.0, 141.2, 141.2, 128.8, 127.4, 126.7, 126.7, 121.9, 121.9, 72.4, 72.1, 68.0, 68.0, 41.6, 41.1, 38.2, 37.5. HRMS-ESI+: calculated for [M+H+] = 241.1335, observed [M+H+] = 241.1329. 2-Phenyl-1-(2-phenylaziridin-1-yl)propan-2-ol (105l) Prepared from α-methyl styrene (104l, 19.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1.4:1 mixture of two diastereomers as a pale yellow liquid (10.5 mg, 41% yield).1H NMR (400 MHz, CDCl3): δ 7.65– 7.41 (m, 2H), 7.39–7.27 (m, 6H), 7.25–6.99 (m, 7H), 7.01–6.74 (m, 1H), 3.80 (br, 1H), 3.75 (br, 1H), 2.96 (d, J = 11.8 Hz, 1H), 2.76 (d, J = 2.0 Hz, 2H), 2.58 (d, J = 11.8 Hz, 1H), 2.45 (dd, J = 6.5, 3.4 Hz, 1H), 2.10 (dd, J = 6.5, 3.5 Hz, 1H), 1.95 (d, J = 3.4 Hz, 1H), 1.78 (d, J = 6.5 Hz, 1H), 1.72 (d, J = 3.5 Hz, 1H), 1.68–1.30 (m, 7H).13C NMR (126 MHz, CDCl3): δ 146.6, 146.5, 139.7, 139.5, 128.3, 128.0, 127.9, 127.9, 127.0, 126.8, 126.6, 126.5, 125.9, 125.9, 124.9, 124.9, 73.7, 73.6, 72.0, 71.8, 41.7, 41.4, 38.1, 37.2, 27.8, 27.7. HRMS-ESI+: calculated for [M+H+] = 254.1539, observed [M+H+] = 254.1533. 1,1-Diphenyl-2-(2-phenylaziridin-1-yl)ethan-1-ol (105m) Prepared from ethene-1,1- diyldibenzene (104m, 27.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin- 1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as an off white solid (13.8 mg, 44% yield).1H NMR (400 MHz, CDCl3): δ 7.58–7.44 (m, 2H), 7.42–7.37 (m, 2H), 7.35–7.30 (m, 2H), 7.26–7.12 (m, 7H), 7.01– 6.91 (m, 2H), 4.52 (s, 1H), 3.37 (d, J = 11.8 Hz, 1H), 3.26 (d, J = 11.7 Hz, 1H), 2.30 (dd, J = 6.5, 3.5 Hz, 1H), 1.83 (d, J = 3.5 Hz, 1H), 1.72 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 145.6, 145.5, 139.4, 128.0, 128.0, 127.9, 126.9, 126.8, 126.7, 126.1, 126.1, 125.9, 77.2, 69.8, 41.6, 37.9. HRMS-ESI+: calculated for [M+H+] = 316.1696, observed [M+H+] = 316.1690. Methyl 2-(1-(4-(1-hydroxy-2-(2-phenylaziridin-1-yl)ethyl)benzoyl)-5-methoxy-2-methyl-1H- indol-3-yl)acetate (105n) Prepared from methyl 2-(5-methoxy-2-methyl-1-(4-vinylbenzoyl)-1H- indol-3-yl)acetate (104n, 54.0 mg, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2- phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as an off white solid (24.0 mg, 48% yield).1H NMR (400 MHz, CDCl3): δ 7.69 (d, J = 8.1 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.41–7.16 (m, 9H), 6.95 (d, J = 2.5 Hz, 1H), 6.88 (dd, J = 9.1, 1.8 Hz, 1H), 6.64 (dd, J = 9.0, 2.4 Hz, 1H), 4.97 (dd, J = 8.8, 3.5 Hz, 1H), 3.83 (s, 2H), 3.69 (d, J = 13.2 Hz, 5H), 2.92 (dd, J = 12.0, 8.8 Hz, 1H), 2.60– 2.44 (m, 2H), 2.37 (s, 3H), 2.01 (d, J = 3.3 Hz, 1H), 1.84 (d, J = 6.8 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 8.2 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.38–7.27 (m, 4H), 7.24–7.14 (m, 5H), 6.95 (d, J = 2.5 Hz, 1H), 6.89 (d, J = 9.0 Hz, 1H), 6.65 (dd, J = 9.0, 2.5 Hz, 1H), 4.99 (dd, J = 8.6, 3.6 Hz, 1H), 3.84 (s, 2H), 3.70 (s, 3H), 3.67 (s, 2H), 2.89 (dd, J = 11.9, 8.7 Hz, 1H), 2.56 (dd, J = 11.9, 3.6 Hz, 1H), 2.50 (dd, J = 6.5, 3.4 Hz, 1H), 2.36 (s, 3H), 1.98 (d, J = 3.4 Hz, 1H), 1.82 (d, J = 6.6 Hz, 1H).13C NMR (126 MHz, CDCl3): δ 171.4, 169.2, 155.9, 147.0, 139.3, 136.0, 134.7, 130.9, 130.5, 129.8, 128.3, 127.2, 126.2, 126.0, 115.0, 112.1, 111.5, 101.1, 72.4, 68.1, 55.7, 52.1, 41.4, 37.5, 30.2, 13.3.13C NMR (126 MHz, CDCl3): δ 171.4, 169.2, 155.9, 147.0, 139.4, 136.0, 134.7, 130.9, 130.5, 129.8, 128.4, 128.3, 127.2, 126.2, 126.2, 126.0, 115.0, 112.1, 111.5, 101.1, 72.6, 68.1, 55.7, 52.1, 41.1, 38.2, 29.6, 13.3. HRMS-ESI+: calculated for [M+H+] = 499.2227, observed [M+H+] = 499.2217. 4-(1-hydroxy-2-(2-phenylaziridin-1-yl)ethyl)benzyl 2-(4-isobutylphenyl)propanoate (105o) Prepared from 4-vinylbenzyl 2-(4-isobutylphenyl)propanoate (104o, 48.0 mg, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1-ium tetrafluoroborate (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as an off white solid (24.7 mg, 54% yield).1H NMR (400 MHz, CDCl3): δ 7.37–7.24 (m, 5H), 7.26–7.14 (m, 6H), 7.09 (d, J = 7.8 Hz, 2H), 5.08 (d, J = 5.6 Hz, 2H), 4.88 (dd, J = 9.0, 3.5 Hz, 1H), 3.74 (q, J = 7.2 Hz, 1H), 3.36 (br, 1H), 2.83 (dd, J = 12.0, 8.9 Hz, 1H), 2.46 (t, J = 6.4 Hz, 4H), 1.95 (d, J = 3.5 Hz, 1H), 1.85 (p, J = 6.7 Hz, 1H), 1.77 (d, J = 6.5 Hz, 1H), 1.51 (d, J = 7.3 Hz, 3H), 0.90 (d, J = 6.7 Hz, 6H).1H NMR (400 MHz, CDCl3): δ 7.30 (dd, J = 7.8, 3.5 Hz, 4H), 7.24–7.13 (m, 6H), 7.08 (d, J = 7.8 Hz, 3H), 5.33–4.99 (m, 2H), 4.86 (dd, J = 9.2, 3.4 Hz, 1H), 3.74 (q, J = 7.1 Hz, 1H), 3.31 (br, 1H), 2.92 (dd, J = 12.0, 9.1 Hz, 1H), 2.67–2.22 (m, 5H), 1.99 (d, J = 3.4 Hz, 1H), 1.84 (m, 2H), 1.50 (d, J = 7.2 Hz, 3H), 0.90 (d, J = 6.6 Hz, 6H).13C NMR (101 MHz, CDCl3): δ 141.6, 140.5, 139.5, 137.5, 135.3, 129.2, 128.2, 127.8, 127.1, 127.0, 126.0, 126.0, 72.6, 68.4, 66.0, 45.1, 45.0, 41.3, 37.3, 30.1, 22.3, 18.4.13C NMR (101 MHz, CDCl3): δ 174.5, 141.6, 140.5, 139.6, 137.5, 135.4, 129.3, 128.3, 127.8, 127.2, 127.0, 126.0, 126.0, 72.8, 68.4, 66.0, 45.1, 45.0, 41.1, 38.0, 30.1, 22.3, 18.4. HRMS-ESI+: calculated for [M+H+] = 458.2690, observed [M+H+] = 458.2680. 2-(2-(4-Fluorophenyl)aziridin-1-yl)-1-phenylethan-1-ol (105p) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-(4-fluorophenyl)aziridin-1-yl)-2,4,6- triphenylpyridine-1-ium tetrafluoroborate (102b, 53.0, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.0 mg, 62% yield).1H NMR (400 MHz, CDCl3): δ 7.27–7.21 (m, 5H), 7.10–7.07 (m, 2H), 6.93–6.89 (m, 2H), 4.82 (dd, J = 8.8, 3.5 Hz, 1H), 3.24 (br, 1H), 2.77 (dd, J = 12.0, 8.7 Hz, 1H), 2.45 (dd, J = 12.0, 3.5 Hz, 1H), 2.37 (dd, J = 6.5, 3.4 Hz, 1H), 1.82 (d, J = 3.4 Hz, 1H), 1.68 (d, J = 6.5 Hz, 1H) ppm.1H NMR (400 MHz, CDCl3): δ 7.37–7.31 (m, 5H), 7.19–7.17 (m, 2H), 7.01–6.97 (m, 1H), 4.87 (dd, J = 8.9, 3.6 Hz, 1H), 3.22 (br,1H), 2.94 (dd, J = 12.1, 9.0 Hz, 1H), 2.54–2.35 (m, 2H), 1.95 (d, J = 3.4 Hz, 1H), 1.82 (d, J = 6.5 Hz, 1H) ppm.13C NMR (101 MHz, CDCl3): δ 162.0 (d, J = 243.0 Hz), 141.7, 135.3 (d, J = 2.5 Hz),128.3, 127.6, 127.5, 125.9, 115.1 (d, J = 21.2 Hz), 72.9, 68.4, 40.7, 37.2.13C NMR (101 MHz, CDCl3): δ 162.0 (d, J = 243.0 Hz), 141.7, 135.4 (d, J = 3.7 Hz), 128.3, 127.6, 127.5 (d, J = 8.7 Hz), 126.0, 115.6, 115.0, 73.2, 68.4, 40.4, 38.0. HRMS-ESI+: calculated for [M+H+]= 258.1289, observed [M+H+] = 258.1284. 2-(2-(4-Chlorophenyl)aziridin-1-yl)-1-phenylethan-1-ol (105q) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-(4-chlorophenyl)aziridin-1-yl)-2,4,6- triphenylpyridine-1-ium tetrafluoroborate (102c, 54.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.0 mg, 59% yield).1H NMR (400 MHz, CDCl3): δ 7.27–7.24 (m, 4H), 7.22–7.18 (m, 3H), 7.05 (d, J = 8.6 Hz, 1H), 4.82 (dd, J = 8.6, 3.5 Hz, 1H), 3.17 (br, 1H), 2.75 (dd, J = 12.0, 8.6 Hz, 1H), 2.47 (dd, J = 12.0, 3.5 Hz, 1H), 2.35 (dd, J = 6.5, 3.4 Hz, 1H), 1.82 (d, J = 3.4 Hz, 1H), 1.69 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.37–7.26 (m, 7H), 7.15 (d, J = 8.5 Hz, 2H), 4.87 (dd, J = 8.9, 3.6 Hz, 1H), 3.19 (br, 1H), 2.94 (dd, J = 12.0, 8.8 Hz, 1H), 2.43–2.36 (m, 2H), 1.95 (d, J = 3.3 Hz, 1H), 1.84 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 141.7, 138.2, 132.7, 128.3, 128.3, 127.6, 127.4, 125.9, 72.9, 68.3, 40.7, 37.4.13C NMR (101 MHz, CDCl3): δ 141.7, 138.3, 132.7, 128.4, 128.3, 127.7, 127.3, 125.9, 73.2, 68.4, 40.4, 38.2. HRMS-ESI+: calculated for [M+H+] = 274.0993, observed [M+H+] = 274.0982. 2-(2-(2-Bromophenyl)aziridin-1-yl)-1-phenylethan-1-ol (105r). Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-(2-bromophenyl)aziridin-1-yl)-2,4,6- triphenylpyridine-1-ium tetrafluoroborate (102d, 59.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.8 mg, 53% yield).1H NMR (400 MHz, CDCl3): δ 7.52 (d, J = 3.3 Hz, 1H), 7.39–7.25 (m, 7H), 7.13–7.09 (m, 1H), 4.91 (dd, J = 9.2, 3.5 Hz, 1H), 3.32 (br, 1H), 3.07 (dd, J = 11.9, 9.2 Hz, 1H), 2.84 (dd, J = 6.6, 3.4 Hz, 1H), 2.42 (dd, J = 12.0, 3.5 Hz, 1H), 1.87 (d, J = 3.4 Hz, 1H), 1.84 (d, J = 6.6 Hz, 1H) ppm.1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.0 Hz, 1H), 7.40–7.32 (m, 4H), 7.30–7.27 (m, 3H), 7.13–7.09 (m, 1H), 4.93 (dd, J = 9.0, 3.3 Hz, 1H), 3.24 (br, 1H), 2.92 (dd, J = 12.1, 9.0 Hz, 1H), 2.77 (dd, J = 6.6, 3.4 Hz, 1H), 2.56 (dd, J = 12.1, 3.3 Hz, 1H), 1.93 (d, J = 3.4 Hz, 1H), 1.90 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 141.6, 138.7, 132.2, 128.4, 128.3, 127.7, 127.6, 127.4, 125.9, 123.8, 72.9, 68.3, 41.1, 37.1.13C NMR (101 MHz, CDCl3): δ 141.7, 138.7, 132.2, 128.4, 128.3, 127.6, 127.5, 127.4, 125.9, 123.8, 73.3, 68.3, 41.1, 37.7. HRMS-ESI+: calculated for [M+H+] = 318.0488, observed [M+H+] = 318.0483. 1-Phenyl-2-(2-(4-(trifluoromethyl)phenyl)aziridin-1-yl)ethan-1-ol (105s): Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-(4- (trifluoromethyl)phenyl)aziridin-1-yl)pyridine-1-ium tetrafluoroborate (102e, 58.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (15.3 mg, 50% yield).1H NMR (400 MHz, CDCl3): δ 7.56–7.54 (m, 2H), 7.35–7.28 (m, 7H), 4.91 (dd, J = 8.6, 3.5 Hz, 1H), 3.19 (br, 1H), 2.84 (dd, J = 12.0, 8.5 Hz, 1H), 2.59 (dd, J = 12.0, 3.5 Hz, 1H), 2.50 (dd, J = 6.5, 3.4 Hz, 1H), 1.93 (d, J = 3.4 Hz, 1H), 1.83 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.55 (d, J = 8.0 Hz, 2H), 7.41–7.27 (m, 7H), 4.88 (dd, J = 8.8, 3.7 Hz, 1H), 3.05 (br,1H), 2.97 (dd, J = 12.1, 8.7 Hz, 1H), 2.58–2.38 (m, 2H), 1.99 (d, J = 3.2 Hz, 1H), 1.90 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 144.0, 141.7, 129.2 (q, J = 32.2 Hz), 128.4, 127.7, 127.1 (q, J = 274.0 Hz), 126.4, 125.9, 125.2 (q, J = 3.9 Hz), 73.0, 68.3, 40.9, 37.7.13C NMR (101 MHz, CDCl3): δ 144.0, 141.6, 129.2 (q, J = 33.1 Hz), 128.4, 127.7, 127.1 (q, J = 270.0 Hz), 126.3, 126.0, 125.2 (q, J = 3.9 Hz), 73.3, 68.3, 40.6, 38.6. HRMS-ESI+: calculated for [M+H+] = 308.1257, observed [M+H+] = 308.1248. 4-(1-(2-Hydroxy-2-phenylethyl)aziridin-2-yl)benzonitrile (105t) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 4-(1-(2,4,6-triphenyl-pyridin-1-yl)aziridin-2- yl)benzonitrilepyridine-1-ium tetrafluoroborate (102f, 45.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.5 mg, 62% yield).1H NMR (400 MHz, CDCl3): δ 7.49 (d, J = 8.1 Hz, 2H), 7.28–7.14 (m, 7H), 4.83 (dd, J = 8.3, 3.6 Hz, 1H), 3.06 (br,1H), 2.74 (dd, J = 12.1, 8.3 Hz, 1H), 2.55 (dd, J = 12.1, 3.6 Hz, 1H), 2.39 (dd, J = 6.6, 3.3 Hz, 1H), 1.84 (d, J = 3.4 Hz, 1H), 1.77 (d, J = 6.5 Hz, 1H).ppm.1H NMR (400 MHz, CDCl3): δ 7.54–7.45 (m, 2H), 7.33–7.19 (m, 7H), 4.80 (dd, J = 8.6, 3.9 Hz, 1H), 2.89 (dd, J = 12.1, 8.6 Hz, 1H), 2.39 (dd, J = 12.1, 3.9 Hz, 1H), 2.33 (dd, J = 6.5, 3.2 Hz, 1H), 1.90 (d, J = 3.3 Hz, 1H), 1.85 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 145.5, 141.6, 132.0, 128.3, 127.7, 126.8, 125.8, 118.9, 110.6, 72.9, 68.1, 40.9, 38.0.13C NMR (101 MHz, CDCl3): δ 145.6, 141.6, 132.1, 128.4, 127.8, 126.7, 126.0, 118.9, 110.7, 73.3, 68.2, 40.6, 38.9. HRMS-ESI+: calculated for [M+H+] = 265.1335, observed [M+H+] = 265.1326. Ethyl 4-(1-(2-hydroxy-2-phenylethyl)aziridin-2-yl)benzoate (105u) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 4-(1-(2,4,6-triphenyl-pyridin-1-yl)aziridin-2- yl)benzonitrilepyridine-1-ium tetrafluoroborate (102g, 58.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (17.4 mg, 56% yield).1H NMR (400 MHz, CDCl3): δ 8.11–7.78 (m, 2H), 7.45–7.18 (m, 7H), 4.91 (dd, J = 8.6, 3.5 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3.22 (s, 1H), 2.85 (dd, J = 12.0, 8.5 Hz, 1H), 2.58 (dd, J = 12.0, 3.6 Hz, 1H), 2.49 (dd, J = 6.5, 3.3 Hz, 1H), 1.95 (d, J = 3.3 Hz, 1H), 1.83 (d, J = 6.6 Hz, 1H), 1.40 (t, J = 7.1 Hz, 3H).1H NMR (400 MHz, CDCl3): δ 8.02–7.81 (m, 2H), 7.36–7.19 (m, 7H), 4.81 (dd, J = 8.8, 3.7 Hz, 1H), 3.10 (br, 1H), 2.89 (dd, J = 12.0, 8.8 Hz, 1H), 2.43–2.24 (m, 2H), 1.93 (d, J = 3.2 Hz, 1H), 1.82 (d, J = 6.6 Hz, 1H).13C NMR (126 MHz, CDCl3): δ 166.5, 145.0, 141.7, 129.5, 129.2, 128.3, 127.6, 125.9, 125.8, 72.9, 68.3, 60.8, 41.1, 37.8, 14.3.13C NMR (126 MHz, CDCl3): δ 166.4, 145.1, 141.6, 129.6, 129.2, 128.3, 127.7, 126.0, 125.9, 73.2, 68.4, 60.8, 40.8, 38.6, 14.3. HRMS- ESI+: calculated for [M+H+] = 312.1594, observed [M+] = 312.1585. 2-(2-(3-Nitrophenyl)aziridin-1-yl)-1-phenylethan-1-ol (105v) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-(3-nitrophenyl)aziridin-1-yl)-2,4,6-triphenylpyridine- 1-ium tetrafluoroborate (102h, 56.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as yellow liquid (11.3 mg, 40% yield).1H NMR (400 MHz, CDCl3): δ 8.10– 8.07 (m, 1H), 8.04 (t, J = 2.0 Hz, 1H), 7.55–7.40 (m, 2H), 7.38–7.27 (m, 5H), 4.93 (dd, J = 8.3, 3.5 Hz, 1H), 2.84 (dd, J = 12.0, 8.3 Hz, 1H), 2.65 (dd, J = 12.0, 3.5 Hz, 1H), 2.53 (dd, J = 6.5, 3.3 Hz, 1H), 1.96 (d, J = 3.3 Hz, 1H), 1.85 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 8.19– 8.05 (m, 1H), 8.05 (s, 1H), 7.53–7.42 (m, 2H), 7.41–7.27 (m, 5H), 4.90 (dd, J = 8.5, 4.0 Hz, 1H), 2.98 (dd, J = 12.1, 8.5 Hz, 1H), 2.60–2.36 (m, 2H), 2.01 (d, J = 3.2 Hz, 1H), 1.92 (d, J = 6.5 Hz, 1H).13C NMR (126 MHz, CDCl3): δ 148.3, 142.2, 141.7, 132.2, 129.1, 128.3, 127.7, 125.8, 122.0, 121.2, 72.9, 68.2, 40.6, 37.6.13C NMR (126 MHz, CDCl3): δ 148.3, 142.3, 141.6, 132.0, 129.2, 128.4, 127.8, 126.0, 122.0, 121.1, 73.3, 68.2, 40.2, 38.6. HRMS-ESI+: calculated for [M+H+] = 285.1234, observed [M+H+] = 285.1227. (1S)-1-Phenyl-2-(2-(p-tolyl)aziridin-1-yl)ethan-1-ol (105w) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 2,4,6-triphenyl-1-(2-(p-tolyl)aziridin-1-yl)pyridine-1-ium tetrafluoroborate (102i, 52.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (11.1 mg, 44% yield).1H NMR (400 MHz, CDCl3): δ 7.38– 7.31(m, 3H), 7.29–7.26 (m, 2H), 7.15–7.11 (m, 4H), 4.87 (dd, J = 9.1, 3.4 Hz, 1H), 3.36 (br, 1H), 2.94 (dd, J = 11.9, 9.1 Hz, 1H), 2.42-2.34 (m, 5H), 1.98 (d, J = 3.4 Hz, 1H), 1.81 (d, J = 6.4 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.40–7.28 (m, 5H), 7.11 (m, 4H), 4.90 (dd, J = 9.1, 3.4 Hz, 1H), 3.35 (br, 1H), 2.86 (dd, J = 12.0, 9.1 Hz, 1H), 2.55–2.41 (m, 1H), 2.33 (s, 4H), 1.93 (d, J = 3.6 Hz, 1H), 1.75 (d, J = 6.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 141.8, 136.7, 136.5, 128.9, 128.3, 127.5, 126.0, 125.9, 72.9, 68.5, 41.1, 37.2, 21.0.13C NMR (101 MHz, CDCl3): δ 141.7, 136.7, 136.7, 129.0, 128.3, 127.6, 125.9, 125.9, 73.1, 68.6, 40.9, 37.8, 21.0. HRMS-ESI+: calculated for [M+H+] = 254.1539, observed [M+H+] = 254.1530. 2-(2-([1,1'-Biphenyl]-4-yl)aziridin-1-yl)-1-phenylethan-1-ol (105x) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-([1,1'-biphenyl]-4-yl)aziridin-1-yl)-2,4,6- triphenylpyridine-1-ium tetrafluoroborate (102j, 59.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (13.2 mg, 42% yield).1H NMR (400 MHz, CDCl3): δ 7.60–7.53 (m, 4H), 7.46–7.42 (m, 2H), 7.38–7.27 (m, 8H), 4.93 (dd, J = 9.0, 3.4 Hz, 1H), 3.32 (br, 1H), 2.89 (dd, J = 11.9, 9.0 Hz, 1H), 2.55–2.51 (m, 2H), 2.00 (d, J = 3.4 Hz, 1H), 1.81 (d, J = 6.6 Hz, 1H) ppm.13C NMR (101 MHz, CDCl3): δ 141.8, 140.9, 140.0, 138.7, 128.7, 128.3, 127.6, 127.1, 127.0, 127.0, 126.5, 125.9, 72.9, 68.5, 41.0, 37.4. HRMS-ESI+: calculated for [M+H+] = 316.1696, observed [M+H+] = 316.1688. 2-(2-(Naphthalen-2-yl)aziridin-1-yl)-1-(3-nitrophenyl)ethan-1-ol (105y) Prepared from 1- nitro-3-vinylbenzene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-(naphthalen-2-yl)aziridin- 1-yl)-2,4,6-triphenylpyridine-1-ium tetrafluoroborate (102k, 56.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (23.0 mg, 69% yield).1H NMR (400 MHz, CDCl3): δ 8.22 (d, J = 2.1 Hz, 1H), 8.09 (m, 1H), 7.86–7.72 (m, 3H), 7.71–7.63 (m, 1H), 7.53–7.33 (m, 3H), 7.32–7.20 (m, 2H), 5.02 (dd, J = 8.1, 3.8 Hz, 1H), 2.84 (dd, J = 12.0, 8.1 Hz, 1H), 2.72 (dd, J = 12.0, 3.8 Hz, 1H), 2.58 (dd, J = 6.6, 3.5 Hz, 1H), 2.09 (d, J = 3.4 Hz, 1H), 1.89 (d, J = 6.6 Hz, 1H).1H NMR (500 MHz, CDCl3): δ 8.27 (s, 1H), 8.19–8.02 (m, 1H), 7.94–7.65 (m, 5H), 7.47 (m, 3H), 7.31 (dd, J = 8.4, 1.8 Hz, 1H), 5.01 (dd, J = 8.7, 3.8 Hz, 1H), 3.58 (br, 1H), 3.00 (m, 1H), 2.73–2.56 (m, 1H), 2.52 (dd, J = 12.1, 3.8 Hz, 1H), 2.11 (d, J = 3.4 Hz, 1H), 1.91 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 148.2, 144.1, 136.6, 133.2, 132.7, 132.0, 129.2, 128.1, 127.6, 127.5, 127.5, 126.2, 126.2, 125.6, 124.9, 123.8, 123.7, 122.4, 121.0, 71.9, 68.0, 41.9, 37.3.13C NMR (101 MHz, CDCl3): δ 148.2, 144.0, 136.8, 133.2, 132.8, 132.1, 129.2, 128.2, 127.7, 127.5, 126.2, 125.7, 124.9, 123.8, 122.5, 121.1, 72.2, 68.0, 41.6, 38.0. HRMS-ESI+: calculated for [M+H+] = 335.1390, observed [M+H+] = 335.1378. 2-(2-(Benzo[b]thiophen-2-yl)aziridin-1-yl)-1-phenylethan-1-ol (105z) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-(2-(benzo[b]thiophen-6-yl)aziridin-1-yl)-2,4,6- triphenylpyridine-1-ium tetrafluoroborate (102l, 57.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (16.8 mg, 57% yield).1H NMR (400 MHz, CDCl3): δ 7.85–7.74 (m, 1H), 7.74–7.58 (m, 1H), 7.44–7.27 (m, 7H), 7.16 (s, 1H), 4.95 (dd, J = 8.7, 3.5 Hz, 1H), 3.22 (br, 1H), 2.87–2.72 (m, 2H), 2.65 (dd, J = 12.0, 3.6 Hz, 1H), 2.12 (d, J = 3.3 Hz, 1H), 1.85 (d, J = 6.4 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.80–7.73 (m, 1H), 7.72–7.64 (m, 1H), 7.45–7.27 (m, 7H), 7.18 (s, 1H), 4.94 (dd, J = 9.0, 3.5 Hz, 1H), 3.26 (br, 1H), 2.99 (dd, J = 12.1, 9.0 Hz, 1H), 2.76 (dd, J = 6.4, 3.3 Hz, 1H), 2.43 (dd, J = 12.1, 3.5 Hz, 1H), 2.19 (d, J = 3.2 Hz, 1H), 1.93 (d, J = 6.3 Hz, 1H).13C NMR (126 MHz, CDCl3): δ 145.3, 141.7, 139.9, 138.8, 128.3, 127.6, 125.9, 124.2, 123.8, 122.9, 122.3, 120.6, 73.0, 68.2, 38.2, 37.9.13C NMR (126 MHz, CDCl3): δ 145.4, 141.6, 140.0, 138.8, 128.4, 127.7, 126.0, 124.3, 123.9, 122.9, 122.3, 120.5, 73.2, 68.2, 38.7, 37.7. HRMS-ESI+: calculated for [M+H+] = 296.1104, observed [M+H+] = 296.1099. 4-(1-(2-Hydroxy-2-phenylethyl)aziridin-2-yl)benzyl 2-(1-(4-chlorobenzoyl)-5-methoxy-2- methyl-1H-indol-3-yl)acetate (105aa) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 4-(1-(2,4,6-triphenylpyridin-1-yl)aziridin-2-yl)benzyl 2-(1-(4-chlorobenzoyl)-5- methoxy-2-methyl-1H-indol-3-yl)acetate tetrafluoroborate (102m, 88.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (29.0 mg, 48% yield). δ1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.5 Hz, 2H), 7.46 (d, J = 8.5 Hz, 2H), 7.41 – 7.22 (m, 7H), 7.17 (d, J = 8.1 Hz, 2H), 6.98 – 6.81 (m, 2H), 6.67 (dd, J = 9.0, 2.6 Hz, 1H), 5.12 (s, 2H), 4.90 (dd, J = 9.3, 3.3 Hz, 1H), 3.77 (s, 3H), 3.70 (s, 2H), 3.29 (br, 1H), 2.85 (dd, J = 12.0, 8.9 Hz, 1H), 2.55 – 2.43 (m, 2H), 2.36 (s, 3H), 1.92 (d, J = 3.4 Hz, 1H), 1.78 (d, J = 6.5 Hz, 1H).1H NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.5 Hz, 2H), 7.46 (d, J = 8.5 Hz, 2H), 7.39 – 7.14 (m, 9H), 7.03 – 6.77 (m, 2H), 6.67 (dd, J = 9.0, 2.6 Hz, 1H), 5.12 (s, 2H), 4.86 (dd, J = 9.1, 3.4 Hz, 1H), 3.77 (s, 3H), 3.70 (s, 2H), 3.27 (br, 1H), 2.95 (dd, J = 12.0, 9.1 Hz, 1H), 2.51 – 2.26 (m, 6H), 1.98 (d, J = 3.3 Hz, 1H), 1.85 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 170.6, 168.2, 156.0, 141.7, 140.0, 139.2, 135.9, 134.5, 133.8, 131.1, 130.7, 130.5, 129.1, 128.3, 128.2, 127.6, 126.2, 125.9, 114.9, 112.4, 111.8, 101.1, 72.9, 68.4, 66.5, 55.6, 41.0, 37.4, 30.4, 13.3.13C NMR (126 MHz, CDCl3): δ 170.6, 168.2, 156.0, 141.6, 140.1, 139.2, 135.9, 134.5, 133.8, 131.1, 130.7, 130.5, 129.1, 128.3, 128.3, 127.6, 126.2, 125.9, 114.9, 112.4, 111.8, 101.1, 73.2, 68.5, 66.5, 55.6, 40.7, 38.2, 30.4, 13.3. HRMS-ESI+: calculated for [M+H+] = 609.2151, observed [M+H+] = 609.21412. Methyl 2-((3-(1-(2-hydroxy-2-phenylethyl)aziridin-2-yl)-2-methylphenyl)amino)-benzoate (105ab) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-methyl-2-((2- methyl-3-(1-(2,4,6-triphenylpyridin-1-yl)aziridin-2-yl)phenyl)amino)benzoate tetrafluoroborate (102n, 67.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (26.0 mg, 65% yield).1H NMR (400 MHz, CDCl3): δ 9.25 (s, 1H), 7.96 (dd, J = 8.0, 1.7 Hz, 1H), 7.61–7.29 (m, 5H), 7.24–7.03 (m, 4H), 6.76 (dd, J = 8.6, 1.1 Hz, 1H), 6.70–6.66 (m, 1H), 4.94 (dd, J = 9.1, 3.4 Hz, 1H), 3.92 (s, 3H), 3.41 (br, 1H), 3.04 (dd, J = 11.9, 9.2 Hz, 1H), 2.64 (dd, J = 6.6, 3.6 Hz, 1H), 2.43 (dd, J = 11.9, 3.4 Hz, 1H), 2.27 (s, 3H), 1.91 (d, J = 3.5 Hz, 1H), 1.81 (d, J = 6.6 Hz, 1H).1H NMR (500 MHz, CDCl3): δ 9.26 (s, 1H), 7.97 (dd, J = 8.1, 1.7 Hz, 1H), 7.46–7.38 (m, 2H), 7.38–7.32 (m, 2H), 7.31–7.15 (m, 5H), 6.78 (dd, J = 8.5, 1.1 Hz, 1H), 6.68 (m, 1H), 4.95 (dd, J = 8.9, 3.4 Hz, 1H), 3.92 (s, 3H), 3.37 (br, 1H), 2.92 (dd, J = 12.1, 8.9 Hz, 1H), 2.64–2.49 (m, 2H), 2.30 (s, 3H), 1.92 (d, J = 3.4 Hz, 1H), 1.86 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3): δ 169.1, 149.2, 141.8, 139.3, 138.7, 134.1, 131.9, 131.4, 128.3, 127.6, 126.4, 125.9, 123.9, 122.8, 116.2, 113.7, 110.9, 73.3, 68.6, 51.7, 39.7, 37.2, 13.3.13C NMR (101 MHz, CDCl3): δ 169.1, 149.2, 141.7, 139.2, 138.7, 134.1, 132.2, 131.4, 128.3, 127.6, 126.3, 125.9, 124.0, 122.9, 116.2, 113.6, 110.9, 72.9, 68.6, 51.7, 39.6, 36.4, 13.4. HRMS-ESI+: calculated for [M+H+] = 403.2016, observed [M+H+] = 403.2008. 4-(1-(2-Hydroxy-2-phenylethyl)aziridin-2-yl)benzyl-2-(4-isobutylphenyl)propanoate (105ac) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 1-methyl-4-(1-(2,4,6- triphenylpyridin-1-yl)aziridin-2-yl)benzyl 2-(4-isobutylphenyl)propanoate tetrafluoroborate (102o, 73.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (29.0 mg, 63% yield).1H NMR (400 MHz, CDCl3): δ 7.39–7.27 (m, 4H), 7.23–7.06 (m, 9H), 5.21–4.97 (m, 2H), 4.90 (dd, J = 8.9, 3.4 Hz, 1H), 3.74 (q, J = 7.2 Hz, 1H), 3.29 (br, 1H), 2.85 (dd, J = 11.9, 8.9 Hz, 1H), 2.60–2.38 (m, 4H), 1.92 (d, J = 3.4 Hz, 1H), 1.85 (m, 1H), 1.77 (d, J = 6.5 Hz, 1H), 1.51 (d, J = 7.2 Hz, 3H), 0.91 (d, J = 6.6 Hz, 6H).1H NMR (400 MHz, CDCl3): δ 7.42–7.26 (m, 5H), 7.24–7.02 (m, 8H), 5.15–5.00 (m, 2H), 4.86 (dd, J = 9.2, 3.4 Hz, 1H), 3.74 (q, J = 7.2 Hz, 1H), 3.26 (br, 1H), 2.94 (dd, J = 12.0, 9.1 Hz, 1H), 2.45 (d, J = 7.2 Hz, 2H), 2.43– 2.35 (m, 2H), 1.97 (d, J = 3.3 Hz, 1H), 1.90–1.80 (m, 2H), 1.50 (d, J = 7.2 Hz, 3H), 0.90 (d, J = 6.6 Hz, 6H).13C NMR (101 MHz, CDCl3): δ 174.5, 141.7, 140.5, 139.6, 137.5, 134.9, 129.2, 128.3, 127.8, 127.6, 127.2, 126.1, 125.9, 72.9, 68.4, 66.1, 45.1, 45.0, 41.0, 37.4, 30.1, 22.3, 18.4.. 13C NMR (126 MHz, CDCl3): δ 174.5, 141.6, 140.5, 139.7, 137.5, 134.9, 129.3, 129.3, 128.3, 127.9, 127.6, 127.2, 126.1, 125.9, 73.1, 68.5, 66.1, 45.1, 45.0, 40.8, 38.1, 30.1, 22.3, 18.4. HRMS-ESI+: calculated for [M+H+] = 458.2690, observed [M+H+] = 458.2676. 4-(1-(2-Hydroxy-2-phenylethyl)aziridin-2-yl)benzyl 4-(N,N-dipropylsulfamoyl)benzoate (105ad) Prepared from styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and 4-(1-(2,4,6- triphenylpyridin-1-yl)aziridin-2-yl)benzyl-4-(N,N-dipropylsulfamoyl)benzoate tetrafluoroborate (102p, 81.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a 1:1 mixture of two diastereomers as a yellow liquid (31.6 mg, 59% yield).1H NMR (400 MHz, CDCl3): δ 8.17 (dd, J = 8.5, 1.9 Hz, 2H), 7.98–7.77 (m, 2H), 7.46–7.18 (m, 9H), 5.36 (s, 2H), 4.90 (dd, J = 8.9, 3.3 Hz, 1H), 3.35–2.95 (m, 4H), 2.85 (dd, J = 11.9, 9.0 Hz, 1H), 2.67–2.36 (m, 2H), 1.94 (d, J = 3.3 Hz, 1H), 1.79 (dd, J = 6.6, 1.7 Hz, 1H), 1.54 (m, 4H), 0.86 (m, 6H)..1H NMR (400 MHz, CDCl3): δ 8.24–8.11 (m, 2H), 7.86 (dt, J = 8.6, 2.0 Hz, 2H), 7.54–7.09 (m, 9H), 5.36 (s, 2H), 4.86 (dd, J = 9.1, 3.2 Hz, 1H), 3.29 (br, 1H), 3.18–3.02 (m, 4H), 2.95 (dd, J = 12.0, 9.2 Hz, 1H), 2.43 (m, 2H), 2.00 (d, J = 3.2 Hz, 1H), 1.86 (d, J = 6.6 Hz, 1H), 1.54 (m, 4H), 0.86 (t, J = 7.4 Hz, 6H).13C NMR (101 MHz, CDCl3): δ 165.0, 144.3, 141.7, 140.2, 134.2, 133.4, 130.2, 128.5, 128.3, 127.6, 126.9, 126.4, 125.9, 72.9, 68.4, 67.1, 49.8, 41.0, 37.4, 21.8, 11.1.13C NMR (126 MHz, CDCl3): δ 165.1, 144.3, 141.6, 140.4, 134.3, 133.4, 130.3, 128.6, 128.5, 128.4, 127.7, 127.0, 126.4, 126.0, 126.0, 73.2, 68.5, 68.1, 49.9, 40.8, 38.2, 21.9, 11.1. HRMS-ESI+: calculated for [M+H+] = 537.2418, observed [M+H+] = 537.2410. EXAMPLE 15 Various example compounds are found in FIG.49. 2-(7-Azabicyclo[4.1.0]heptan-7-yl)-1-phenylethan-1-ol (107a) Prepared from styrene 104a (17.0 µL, 0.150 mmol, 1.50 equiv) and 7-(2,4,6-triphenyl-pyridin-1-yl)-7- azabicyclo[4.1.0]heptane tetrafluoroborate 106 (49.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a yellow liquid (9.5 mg, 42% yield).1H NMR (400 MHz, CDCl3): δ1H NMR (400 MHz, CDCl3) δ 7.65–7.17 (m, 5H), 4.79 (dd, J = 9.0, 3.6 Hz, 1H), 3.69 (br, 1H), 2.74 (dd, J = 11.9, 9.0 Hz, 1H), 2.19 (dd, J = 11.9, 3.6 Hz, 1H), 1.91–1.58 (m, 6H), 1.36 (m, 2H), 1.28–1.11 (m, 2H).13C NMR (101 MHz, CDCl3): δ 142.1, 128.2, 127.3, 125.9, 72.7, 68.1, 38.4, 38.1, 24.5, 24.2, 20.4, 20.3. HRMS-ESI+: calculated for [M+H+] = 218.1539, observed [M+H+] = 218.1534. 2-(7-Azabicyclo[4.1.0]heptan-7-yl)-1-(p-tolyl)ethan-1-ol (107b) Prepared from 1-methyl-4- vinylbenzene 104b (20.0 µL, 0.150 mmol, 1.50 equiv) and 7-(2,4,6-triphenyl-pyridin-1-yl)-7- azabicyclo[4.1.0]heptane tetrafluoroborate 106 (49.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a yellow liquid (8.0 mg, 33% yield).1H NMR (400 MHz, CDCl3): δ 7.49–7.20 (m, 2H), 7.14 (d, J = 7.8 Hz, 2H), 4.76 (dd, J = 9.2, 3.5 Hz, 1H), 3.63 (br, s), 2.74 (dd, J = 11.8, 9.2 Hz, 1H), 2.33 (s, 3H), 2.15 (dd, J = 11.9, 3.6 Hz, 1H), 1.84–1.67 (m, 4H), 1.66–1.56 (m, 2H), 1.36 (m, 2H), 1.24–1.07 (m, 2H).13C NMR (126 MHz, CDCl3): δ 139.1, 137.0, 128.9, 125.8, 72.6, 68.1, 38.3, 38.1, 24.5, 24.2, 21.1, 20.4, 20.3. HRMS-ESI+: calculated for [M+H+] = 232.1696, observed [M+H+] = 232.1693. 2-(7-Azabicyclo[4.1.0]heptan-7-yl)-1-(2-bromophenyl)ethan-1-ol (107c) Prepared from 1- bromo-2-vinylbenzene 104f (19.0 µL, 0.150 mmol, 1.50 equiv) and 7-(2,4,6-triphenyl-pyridin-1- yl)-7-azabicyclo[4.1.0]heptane tetrafluoroborate 106 (49.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a yellow liquid (14.2 mg, 48% yield).1H NMR (400 MHz, CDCl3): δ 7.66 (dd, J = 7.7, 1.7 Hz, 1H), 7.47 (dd, J = 7.9, 1.2 Hz, 1H), (m, 1H), 5.09 (dd, J = 8.4, 3.2 Hz, 1H), 4.03 (br, 1H), 2.62 (dd, J = 11.9, 8.4 Hz, 1H), 2.34 (dd, J = 11.9, 3.3 Hz, 1H), 1.90–1.60 (m, 5H), 1.56 (m, 1H), 1.36 (m, 2H), 1.20 (m, 2H).13C NMR (126 MHz, CDCl3): δ 141.0, 132.3, 128.6, 127.7, 127.5, 121.5, 71.4, 65.6, 38.7, 37.8, 24.5, 24.1, 20.4, 20.3. HRMS-ESI+: calculated for [M+H+] = 296.0645, observed [M+H+] = 296.0642. 2-(7-Azabicyclo[4.1.0]heptan-7-yl)-1-(3-nitrophenyl)ethan-1-ol (107d) Prepared from 1-nitro- 3-vinylbenzene 104j (19.0 µL, 0.150 mmol, 1.50 equiv) and 7-(2,4,6-triphenyl-pyridin-1-yl)-7- azabicyclo[4.1.0]heptane tetrafluoroborate 106 (49.0 mg, 0.100 mmol, 1.00 equiv), and obtained as an off white solid (9.2 mg, 35% yield).1H NMR (400 MHz, CDCl3): δ 8.24 (t, J = 2.0 Hz, 1H), 8.12 (m, 1H), 7.76–7.66 (m, 1H), 7.51 (t, J = 7.9 Hz, 1H), 4.90 (dd, J = 8.6, 3.7 Hz, 1H), 2.68 (dd, J = 11.9, 8.6 Hz, 1H), 2.35 (dd, J = 11.9, 3.8 Hz, 1H), 1.86–1.62 (m, 6H), 1.36 (m, 2H), 1.24–1.13 (m, 2H).13C NMR (126 MHz, CDCl3): δ 148.2, 144.5, 132.0, 129.2, 122.4, 120.9, 71.5, 67.3, 39.0, 38.5, 24.2, 23.9, 20.2, 20.1. HRMS-ESI+: calculated for [M+H+] = 263.1390, observed [M+H+] = 263.1387. 4-((1S)-2-(7-azabicyclo[4.1.0]heptan-7-yl)-1-hydroxyethyl)benzyl 2-(1-(4-chlorobenzoyl)-5- methoxy-2-methyl-1H-indol-3-yl)acetate (107e) Prepared from 4-vinylbenzyl 2-(1-(4- chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate 104p (71.0 mg, 0.150 mmol, 1.50 equiv) and 7-(2,4,6-triphenyl-pyridin-1-yl)-7-azabicyclo[4.1.0]heptane tetrafluoroborate 106 (49.0 mg, 0.100 mmol, 1.00 equiv), and obtained as an off white solid (11.0 mg, 18% yield).1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.1 Hz, 2H), 7.46 (d, J = 8.2 Hz, 2H), 7.32 (d, J = 8.1 Hz, 1H), 7.28–7.21 (m, 2H), 7.06–6.77 (m, 2H), 6.66 (dd, J = 9.0, 2.6 Hz, 2H), 5.12 (s, 2H), 4.90 (d, J = 9.1 Hz, 1H), 3.76 (s, 3H), 3.70 (s, 2H), 2.67 (dd, J = 12.1, 9.2 Hz, 1H), 2.35 (s, 3H), 1.98–1.68 (m, 7H), 1.39 (dd, J = 13.5, 7.3 Hz, 2H), 1.23–1.07 (m, 2H).13C NMR (126 MHz, CDCl3): δ 170.6, 168.2, 156.0, 142.4, 139.2, 135.9, 134.8, 133.8, 131.1, 130.7, 130.5, 129.1, 128.1, 126.1, 114.9, 112.4, 111.8, 101.1, 72.3, 68.0, 66.5, 55.6, 38.4, 38.2, 30.4, 24.5, 24.2, 20.4, 20.3, 13.3. HRMS- ESI+: calculated for [M+H+] = 587.2307, observed [M+H+] = 587.2298. 2-(Aziridin-1-yl)-1-phenylethan-1-ol (9) Prepared from styrene 104a (17.0 µL, 1.50 equiv, 0.150 mmol) and 1-(aziridin-1-yl)-2,4,6-triphenylpyridin-1-ium trifluoromethanesulfonate 108 (50.0 mg, 0.100 mmol, 1.00 equiv), and obtained as a yellowish liquid (5.2 mg, 25% yield).1H NMR (400 MHz, CDCl3): δ 7.65–7.01 (m, 5H), 4.85 (dd, J = 9.1, 3.4 Hz, 1H), 2.75 (dd, J = 11.9, 9.1 Hz, 1H), 2.22–2.12 (m, 1H), 1.80 (m, 2H), 1.33–1.16 (m, 2H).HRMS-ESI+: calculated for [M+H+] = 164.1070, observed [M+H+] = 164.1069. The obtained spectral data are in good agreement with those reported in literature

[0117] . EXAMPLE 16 C.2 Optimization Studies for Photocatalyzed Olefin Hydroxyaziridination Table 7. Impact of photocatalyst structure on photocatalytic hydroxyaziridination of styrene. entry R yield 1 (Ir[dF(CF3)ppy]2(dtbpy))PF615% 2 [Ir(dtbbpy)(ppy)2]PF626% 3 Ir(ppy)3 35% 4 Ru(bpy)3Cl2.6H2O 16% 5 4-CzIPN 29% 6 Eosin Y 27% Table 8. Impact of solvent on photocatalytic hydroxyaziridination of styrene. 1 DCE 26% 2 THF 22% 3 DMF 14% 4 DMA 19% 5 CH3CN:H2O (1:1) 35% 6 MeOH trace Table 9. Impact of base on photocatalytic hydroxyaziridination of styrene. Table 10. Impact of additives on photocatalytic hydroxyaziridination of styrene. 1 TBAI 35% 2 NaI 52% 3 PIDA 49% 4 LiBr 65% 5aLiBr 42% a50 mol% LiBr was used. EXAMPLE 17 D. Mechanistic Investigations D.1. Examination of Radical Acceptors A 40-mL mg, 0.100 mmol, 1.00 equiv), triphenylpyridinium aziridine 102a (51.0 mg, 0.100 mmol, 1.00 equiv), and Ir(ppy)3(0.7 mg, 0.001 mmol, 1.00 mol%). In an N2-filled dry box, the solid compounds were dissolved in MeCN (1 mL). Into that reaction mixture, Et3N (28.0 µL, 0.200 mmol, 2.00 equiv) was added. With stirring, the reaction was irradiated with blue LED lights for 12 h; the temperature was maintained at 23 ^C using air cooling provided by a fan. The reaction mixture was diluted with distilled water (5.0 mL) and extracted with ethyl acetate (3 × 5.0 mL). The combined organic layer was washed with brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography (hexanes : EtOAc 70:30) to afford the desired aminated olefin 103 via radical addition elimination protocol.1H NMR (400 MHz, CDCl3): δ 7.33–7.05 (m, 5H), 6.20 (d, J = 1.6 Hz, 1H), 5.86 (q, J = 1.9 Hz, 1H), 3.68 (s, 3H), 3.45 (dt, J = 16.5, 1.8 Hz, 1H), 3.04 (dt, J = 16.5, 1.8 Hz, 1H), 2.32 (dd, J = 6.5, 3.4 Hz, 1H), 1.93 (d, J = 3.4 Hz, 1H), 1.75 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 166.7, 139.9, 137.7, 128.3, 126.9, 126.0, 125.8, 60.7, 51.8, 41.6, 38.0. HRMS-ESI+: calculated for [M+H+] = 218.1176, observed [M+H+] = 218.1174. FIG.50 shows a1H NMR spectrum of addition elimination product 103 in CDCl3 (400 MHz) at 23 ^C. D.2. Spin-Trapping Experiments A 25-mL Schlenk tube was charged with triphenylpyridinium aziridine (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), Ir(ppy)3(0.7 mg, 0.001 mmol, 1.00 mol%), and N-tert-butyl-a-phenylnitrone (PBN, 21.2 mg, 0.120 mmol, 1.20 equiv). In an N2-filled dry box, the solid compounds were dissolved in MeCN (1.0 mL) and Et3N (28.0 µL, 0.200 mmol, 2.00 equiv) was added. The resulting solution was irradiated for 2 h with a blue LED. An aliquot of the resulting solution (50 µL) was transferred to a 2 mm EPR tube and the EPR spectrum was collected (FIG.51). FIG.51 shows the EPR radical in the presence of PBN was obtained in CH3CN : (—) Experimental spectrum and (—) simulated spectrum. The observed triplet of quartet in the photolyzed samples is attributed to PBN-trapped aziridnyl radical with aN(PBN)= 14.0 G, aH= 1.8 G, and aN(aziridinyl)= 2.1 G. The apparent triplet of quartet is due to the unresolved / overlapped hyperfine couplings from aHand aN(aziridinyl). Formation of PBN-trapped aziridinyl radical was further confirmed by mass analysis of the EPR sample where HRMS-ESI: calculated for [M+H]+= 295.1805, observed [M+H]+= 295.1797. D.3. Radical Inhibition Experiments A 40-mL scintillation vial was charged with triphenylpyridinium aziridine (102a, 51.0 mg, 0.100 mmol, 1.00 equiv), Ir(ppy)3(0.7 mg, 0.001 mmol, 1.0 mol%), LiBr (8.7 mg, 0.100 mmol, 1.00 equiv) and TEMPO (31.2 mg, 0.200 mmol, 2.00 equiv). The solid compounds were dissolved in a MeCN:H2O (1:1, 2 mL). Into that reaction mixture, styrene (104a, 17.0 µL, 0.150 mmol, 1.50 equiv) and Et3N (28.0 µL, 0.200 mmol, 2.00 equiv) were added. The crude reaction mixture was analysed by1HNMR and HRMS. The analysis of the crude reaction mixture revealed no desired product 105a formation. D.4. Radical Clock Experiments A 40- was mg, 0.100 mmol, 1.00 equiv), Ir(ppy)3(0.7 mg, 0.001 mmol, 1.00 mol%) and LiBr (8.6 mg, 0.100 mmol, 1.00 equiv). The solid compounds were dissolved in a MeCN:H2O (2 mL). Into that reaction mixture, (1-cyclopropylvinyl)benzene (104q)

[0119] (21.6 mg, 0.150 mmol, 1.50 equiv) and Et3N (28.0 µL, 0.200 mmol, 2.00 equiv) were added. The HRMS data of the crude reaction mixture revealed the formation of the amino-hydroxylated product of the olefin along with the cyclopropane ring opened product (110)

[0120] . FIG. 52 shows HRMS data for radical clock reaction. Both the hydroxy-azirinated and ring opened product 110 were observed. D.5. Stern-Volmer Quenching Experiments Fluorescence quenching experiments were performed to identify the primary quencher of the excited photocatalyst

[0121] . A glass cuvette with a B-14 joint and screw cap was used. A solution of Ir(ppy)3in anhydrous CH2Cl2(8.4 × 10-5M) was prepared. An aliquot (2.0 mL) of the stock solution was taken in the glass cuvette and purged with N2. Samples were excited at 360 nm and the emission was collected at 515 nm. The Stern-Volmer analysis was conducted according to the following relationship: ^^0 / ^^ = 1 + [^^] where, I0= fluorescence intensity of photocatalyst (PC) in absence of quencher; I = fluorescence intensity of PC in presence of quencher; [Q] = concentration of quencher; Ksv = quenching rate constant The fluorescence quenching study was performed using pyridinium aziridine 102a, triethylamine as quenchers independently. With increasing concentration of pyridinium salt 102a, an appreciable decrease in the fluorescence intensity of PC was observed, however only a slight decrease in fluorescence intensity was observed upon addition of triethylamine. FIG. 53AA&B shows emission spectra. FIG. 53AA shows emission spectrum of solution of Ir(ppy)3(8.4 × 10-5M) with different concentrations of 102a in MeCN under N2atmosphere at 20 ℃. (—) 0.0 mM, (—) 0.69 mM, (—) 1.03 mM, (—) 1.30 mM, (—) 2.07 mM, and (—) 2.70 mM. FIG. 53AB shows emission spectrum of solution of PC (8.4 × 10-5M) with different concentrations of Et3N in MeCN under N2atmosphere at 20 ℃. (—) 0.0 mM, (—) 0.69 mM, (—) 1.03 mM, (—) 1.30 mM, and (—)2.70 mM. FIG.54 shows aStern-Volmer plot in the quenching study of PC using 102a or Et3N in CH2Cl2under N2atmosphere at 20 ℃ with emission wavelength fixed at 515 nm. Plot of emission intensity ratio using 2a (—) and liner fit (×) vs.2a concentration (R2= 0.91); plot of emission intensity ratio using Et3N (—) and linear fit (×) vs. Et3N concentration (R2= 0.78). D.6. Cyclic Voltammetry of N-pyridinium Aziridine (2a) FIG.55A-D shows cyclic voltammograms. FIG.55A shows a cyclic voltammogram of dissolved molecular oxygen in MeCN. FIG. 55B shows cyclic voltammogram of 2,4,6-triphenyl-1-(2- phenylaziridin-1-yl)pyridin-1-ium (102a) under ambient conditions. FIG. 55C shows a cyclic voltammogram of 2,4,6-triphenyl-1-(2-phenylaziridin-1-yl)pyridin-1-ium (102a) under a nitrogen atmosphere. FIG.55D shows an overlay of the CV data from parts (FIG.55B) and (FIG.55C). CV conditions: substrate 5.00 mM, 0.200 M [TBA]PF6solution of CH3CN, glassy carbon working electrode, Pt counter electrode, and scan rate = 0.10 V / s. ^ EXAMPLE 18 E. X-Ray Diffraction Data FIG. 56 shows displacement ellipsoid plot of 105v plotted at 50% probability. H-atoms are removed for clarity. The crystalline sample used for the diffraction experiment was obtained via pentane diffusion into EtOAc. Table 11. X-ray experimental details of 105v (CCDC 2362719). Crystal data Chemical formula C16H16N2O3Mr284.31 Crystal system, space Monoclinic, P2 / c group1Temperature (K) 100 a, b, c (Å) 25.3664(5), 8.0897(2), 6.9110(2) β (°) 96.433(2) 1409.25(6) 4 Radiation type Cu Kα µ (mm−1) 0.77 Crystal size (mm) 0.18 × 0.03 × 0.01 Data collection Diffractometer XtaLAB Synergy, Dualflex, HyPix Multi-scan Absorption CrysAlis PRO 1.171.43.101a (Rigaku Oxford Diffraction, 2023) Empirical correction absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Tmin, Tmax0.780, 1.000 No. of measured, independent and 10366, 2204, 1996 observed [I > 2σ(I)] reflections Rint0.029 (sin θ / λ)max(Å−1) 0.577 Refinement R[F2> 2σ(F2)], 2 0.049, 0.120, 1.16 2204 No. of parameters 191 H-atom treatment H-atom parameters constrained Δρmax, Δρmin(e Å−3) 0.24, −0.24 FIG. 57 shows a displacement ellipsoid plot of 108 plotted at 50% probability. H-atoms are removed for clarity. The crystalline sample used for the diffraction experiment was obtained via diethylether diffusion into CH3CN. For clarity only one molecule in the unit cell is depicted here. Table 12. X-ray experimental details of 108 (CCDC 2366346). Crystal data Chemical formula 2(CF3O3S)·2(C25H21N2) Mr997.01 Crystal system, space group Triclinic, P–1 (K) 110 a, b, c (Å) 10.876(1), 14.650(2), 14.927(2) α, β, γ (°) 99.836(3), 100.193(4), 98.521(3) V (Å3) 2267.0(5) Z 2 Radiation type Mo Kα µ (mm−1) 0.20 Crystal size (mm) 0.3 × 0.24 × 0.15 Data collection Diffractometer Bruker APEX-II CCD Multi-scan Absorption correction SADABS2016 / 2 (Bruker,2016 / 2) was used for absorption No. of measured, independent and 58688, 9246, 7132 observed [I > 2σ(I)] reflections Rint0.050 (sin θ / λ)max(Å−1) 0.627 Refinement R[F2> 2σ(F2)], wR(F2), S 0.093, 0.223, 1.10 No. of reflections 9246 No. of parameters 665 H-atom treatment H-atom parameters constrained Δρmax, Δρmin(e Å−3) 1.61, −0.93 EXAMPLE 19 F. Optimized Coordinates Table 13. Optimized Coordinates of azirdinyl radical generated from 109.C 0.000000 0.739237 –0.345267C 0.000000 –0.739237 –0.34526755553 HF = –133.269218684 All computations were carried out using Revision C.01 of Gaussian 16 suite of programs

[0122] with the B3LYP [123, 124] functional in conjunction with Grimme’s D3 empirical dispersion

[0125] and Becke-Johnson damping

[0126] . The basis set of 6-31G(d’)

[0127] was used for all atoms. All orbital images were generated using GaussView6

[0128] utilizing an isovalue of 0.1. Thus, specific compositions and methods of synthesis of N-pyridinium and N-aryl aziridines as aspartate and glutamate selective covalent ligands and uses thereof have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. Moreover, in interpreting the disclosure, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms "comprises" and "comprising" should be interpreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced. 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Claims

CLAIMS: We claim:

1. A method of catalyst-free olefin activation in the dark comprising; a) providing; i) an N-aminopyridinium salt; ii) at least one unactivated alkene; and iii) a hypervalent iodine reagent; and b) reacting said unactivated alkene with said N-aminopyridinium in the presence of said hypervalent iodine reagent so as create a pyridinium aziridine compound.

2. The method of Claim 1, wherein said N-aminopyridinium salt has the structure: .

3. The method of Claim 1, wherein said N-aminopyridinium salt has the structure: 6 are independently selected from an aryl group or H.

4. The method of Claim 3, wherein said N-aminopyridinium salt has the structure:

5. The method of Claim 1, wherein said unactivated alkene has the structure: , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substituted R3is an alkyl or substituted alkyl or H.

6. The method of Claim 1, wherein said unactivated alkene comprises an alkene without an electron-withdrawing group directly attached to the double bond.

7. The method of Claim 1, wherein said unactivated alkene comprises a gaseous olefin.

8. The method of Claim 1, wherein said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or H; R2 is an alkyl or substitutedis an alkyl or substituted alkyl or H; and R4-6are independently selected from an aryl group or H.

9. The method of Claim 1, wherein said pyridinium aziridine compound is selected from the group consisting of:N pyMe Npy N py N py N pyn n= 4Me py.

10. The method of Claim 1, wherein said method is metal free.

11. The method of Claim 1, wherein said hypervalent iodine reagent comprises iodosylbenzene.

12. The method of Claim 1, wherein said hypervalent iodine reagent comprises an iminoiodinane.

13. A method of cross coupling a pyridinium aziridine comprising; a) providing; i) a pyridinium aziridine compound; ii) an aryl boronic acid; b) reacting said pyridinium aziridine compound with said aryl boronic acid so as create an aryl-aziridine compound.

14. The method of Claim 13, wherein said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or H; R2 is an alkyl or substitutedis an alkyl or substituted alkyl or H; and R4-6are independently selected from an aryl group or H. B(OH)215. The method of Claim 13, wherein said aryl boronic acid has the .

16. The method of Claim 13, wherein said aryl boronic acid is selected from the group consisting of: .

17. The method of Claim 13, wherein said aryl boronic acid is a substituted aryl boronic acid.

18. The method of Claim 13, wherein said aryl-aziridine compound has the structure , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substituted alk d R3is an alkyl or substituted alkyl or H.

19. The method of Claim 13, wherein said aryl-aziridine compound has the structure selected from the group consisting of: .

20. A method of reductive depyridylation of pyridinium aziridine compound comprising; a) providing;i) said pyridinium aziridine compound; ii) ammonium chloride; and iii) zinc; b) exposing said pyridinium aziridine compound with said ammonium chloride and zinc so as create an N-H-aziridine compound.

21. The method of Claim 20, wherein said pyridinium aziridine compound has the structure: , wherein R1 is an alkyl or substituted alkyl or H; R2 is an alkyl or substitutedis an alkyl or substituted alkyl or H; and R4-6are independently selected from an aryl group or H.

22. The method of Claim 20, wherein said aryl-aziridine compound has the structure selected from the group consisting of:.

23. The method of Claim 20, wherein said N-H-aziridine compound has the , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substitutedR3is an alkyl or substituted alkyl or H.

24. A method comprising; a) providing; i) a compound comprising a clickable aryl aziridine probe; ii) protein; b) reacting said protein with said clickable aryl aziridine probe so as to create a compound- bound protein;c) capturing said compound-bound protein using a click-chemistry compatible structure.

25. The method of Claim 24, wherein said protein comprises at least one aspartate or glutamate residues.

26. The method of Claim 25, wherein said compound-bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein.

27. The method of Claim 24, wherein said clickable aryl aziridine probe has the structure: .

28. The method of Claim 24, wherein said click-chemistry compatible structure comprises a terminal alkyne group.

29. The method of Claim 24, wherein capturing comprising reacting a compound comprising a terminal alkyne group with a terminal azide group.

30. The method of Claim 24, further comprising step d) determining the identity of compound- bound proteins.

31. The method of Claim 24, further comprising step d) determining the structure of compound- bound proteins.

32. The method of Claim 30, wherein determining the identity comprises identification of said protein with mass spectrometry.

33. A method comprising; a) providing; i) an aryl aziridine probe; ii) a protein, wherein said protein is a catalyst; b) reacting said protein with said clickable aryl aziridine probe so as to create a compound- bound protein; and c) measuring the catalytic activity of said compound-bound protein.

34. The method of Claim 33, wherein step d) determining if said catalytic activity of said compound-bound protein is inhibited compared to the catalytic activity of unbound protein.

35. The method of Claim 33, further comprising step d) comparing the catalytic activity of said compound-bound protein at various concentrations.

36. The method of Claim 33, further comprising step d) comparing the catalytic activity of said compound-bound protein to the catalytic activity of compound-bound protein produced by exposure of said protein to a different aryl aziridine probe.

37. The method of Claim 33, wherein said aryl-aziridine probe has the structure , wherein R1is an alkyl or substituted alkyl or H; R2is an alkyl or substituted alk d R3is an alkyl or substituted alkyl or or H.

38. The method of Claim 33, wherein said protein comprises at least one aspartate or glutamate residues.

39. The method of Claim 33, wherein said compound-bound protein is formed by reaction of said aziridine with aspartate or glutamate residues of said protein.

40. The method of Claim 33, wherein said aryl aziridine probe comprises a clickable aryl aziridine probe.

41. A method of N-aziridinyl radical transfer comprising; a) providing; i) an olefin compound; ii) an unsubstituted N-pyridinium aziridine; b) reacting said olefin compound with said unsubstituted N-pyridinium aziridine so as create an hydroxyazirdine compound.

42. The method of Claim 41, wherein said unsubstituted N-pyridinium aziridine compound has thestructure: , wherein R1 is an aryl or substituted aryl; R2 is an aryl, substituted ed alkyl or H; R3is an alkyl or substituted alkyl or H; and R4-8are independently selected from an aryl, substituted aryl, alkyl, substituted alkyl, halogen, bridging group or H.

43. The method of Claim 41, wherein said unsubstituted N-pyridinium aziridine compound has the structure: 8 are independently selected from an aryl, substituted aryl, alkyl,group or H.

44. The method of Claim 41, wherein said reacting further comprises a photocatalyst.

45. The method of Claim 41, wherein said reacting further comprises this use of LiBr.

46. The method of Claim 41, wherein said reacting further comprises this use of Et3N.

47. The method of Claim 41, wherein said olefin has the .

48. The method of Claim 41, wherein said hydroxyazirdine compound is selected from the following: . 5

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