Sulfur ylide diazo compounds and uses thereof

Abstract

The present invention relates to sulfur ylide diazo compounds, their synthesis and their use for the transfer of a carbon atom or a CN2 group into an organic substrate comprising a pi electron system, in particular for C(sp3)-atom transfer to create carbon spiro centers. The invention further relates to related processes and the compounds thus obtained.

Description

[0001] T09015WO SULFUR YLIDE DIAZO COMPOUNDS AND USES THEREOF Technical Field The present invention relates to sulfur ylide diazo compounds, their synthesis and their use for the transfer 5 of a carbon atom or a CN2 group into an organic substrate comprising a pi electron system, in particular for C(sp3)-atom transfer to create carbon spiro centers. The invention further relates to related processes and the compounds thus obtained. Background of the invention 10 The formation of three-dimensional (3D) structures is of fundamental importance in organic chemistry and fragment-based drug discovery. In particular, the quest to create 3D scaffolds such as cubanes, propellanes, bicyclobutanes, or spiro[2.2]pentanes has pushed the development of synthetic methods andtriggered strong interest to deviate from the widely explored two-dimensional landscape. Carbon insertion in the context of skeletal editing in general relates to methods introducing “C‒R” fragments into C(sp2)‒15 C(sp2) bonds typically generating flat, aromatic (hetero)cycles. Pure C-atom transfer reactions, in which a single atom is transferred, include text-book reactions such as the Seyferth‒Gilbert homologation, the Corey‒Fuchs reaction or the Doering‒LaFlamme allene synthesis. Recently, the repertoire for C-atom transfer has been expanded by introducing the phosphorus ylide20 compound Ph3PCN2. However, all of the described methods proceed via an unsaturated carbene / vinylidene intermediate which results in sp-hybridized C-atoms. Hence, three-dimensionality is not generated by these types of C(sp)-atom transfer reactions. Accordingly, C-atom transfer reactions which accomplish the transfer of a C(sp3)-atom still represent an25 unsolved and challenging endeavor, since carbon arc discharge methods, C-atom precursors such as carbon suboxide or diazotetrazole, or chromium carbido complexes, were reported to react unselectively and resulted in only very low yields of C-atom transfer products. A generalizable strategy for precise and high-yielding installation of C(sp3)-atoms to efficiently form four30 new C‒C single bonds therefore remains a major challenge for synthetic chemistry. Summary of the invention The present inventors surprisingly found a to meet this challenge by combining the known C-atom transfer reagents of the general structure X=C=Y with the positive properties of sulfur ylides and diazo compounds35 that are known to exhibit carbene-free cyclopropanation reactivity. Thus, the formation ofcarbene / vinylidene intermediates during the C-atom transfer process could be avoided. Combining both functionalities in one molecule gave access to an ideal reagent for the creation of spiro-C-centers, particularly for the direct formation of spiro[2.2]pentanes in which four new C‒C bonds are created. 40 The newly developed reagents are diazosulfur ylides as described herein below, which have been found to be successfully applicable as a single-step C(sp3)-atom transfer reagent for the construction of C(sp3)-rich, 2 three-dimensional and rigid spirocyclic scaffolds from readily available two-dimensional feedstock molecules. In a first aspect, the present invention therefore relates to a compound of formula (I) or (II) 5 (I) (II)wherein (1) in formula (I), R1= R2or R1≠ R2, wherein R1, R2are selected from substituted or unsubstituted, optionally bridging, groups comprising alkyl, cycloalkyl, aryl, hetaryl, and amine; or 10 (2) in formula (I) or (II), R1and R2are independently of each other selected from alkyl, cycloalkyl, heterocyclyl, aryl, hetaryl, NRcRd, preferably C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, NRcRd, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; or R1and R2combine to form together with the sulfur atom to which they are attached a 5 to 16-15 membered hetaryl or heterocyclyl ring that is unsubstituted or substituted; Rsis selected from O and NRa, wherein each Rais independently selected from S(O)mRe, C1-C12- alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; 20 Rc, Rd, and Reare each independently selected from C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; and m is 1 or 2. 25 In various embodiments of the compound of formula (I) or (II) according to the invention (1) R1and / or R2, preferably both, are selected from unsubstituted or substituted alkyl, cycloalkyl, heterocyclyl, aryl and hetaryl; or (2) R1and R2combine to form together with the sulfur atom to which they are attached a 5 to 16- membered hetaryl or heterocyclyl ring that is monocyclic, bicyclic or tricyclic and is unsubstituted or30 substituted; or (3) R1and / or R2, preferably both, are selected from tert-butyl, adamantyl, unsubstituted or substituted phenyl, unsubstituted or substituted pyrrolyl, and unsubstituted or substituted pyridinyl; or (4) R1and R2combine to form together with the sulfur atom to which they are attached an unsubstituted or substituted ring selected from tetrahydrothiophene, thianthrene, dibenzothiophene, phenothiazine,35 and tetrahydro-4H,9H-thieno[2,3-d:4,5-d']bis([1,3]dioxine. In various embodiments, the compound of formula (I) or (II) according to the invention is selected from the group consisting of: 3

[0002] 5 wherein Rfis C1-C6-alkyl, C3-C6-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, or 5 to 16- membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted. 10 In another aspect, the present invention relates to a process for producing a compound of formula (I) or (II) according to the invention, wherein the process comprises reacting a compound of formula (III) or (IV) wherein each Rpis independently an organic moiety, preferably selected from alkyl, cycloalkyl, heterocyclyl,15 aryl, and hetaryl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, preferably phenyl or alkyl, or wherein two or three Rpcombine to form together with the P atom to which they are attached a 5 to 16-membered hetaryl or heterocyclyl ring that is monocyclic, bicyclic or tricyclic and is unsubstituted or substituted, optionally in presence of a Bronsted base, with nitrous oxide (N2O) to produce the compound of formula (I) or (II). 20 In a further aspect, the present invention relates to a process for the production of compounds of formula (V) or (VI) 4

[0003] (V) (VI)comprising reacting a compound of formula (I) or (II) with an olefin, preferably a compound of formula (Va) or (VIa) 5 (Va) (VIa)wherein R3, R4, R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2- C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered10 heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R3and R4or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are, in all occurrences, unsubstituted or substituted, 15 Rbis selected from C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; and wherein Rc, Rd, Re, and m are defined as described above, wherein, preferably, at least one of R3and R4and / or at least one of R5, R6, R7and R8is not hydrogen. 20 In still another aspect, the present invention relates to a process for the production of compounds of formula (VII), (VIII) or (IX) 25 (VII) (VIII) (IX)comprising reacting a compound of formula (VI) with an olefin, methylenecyclopropane, ketone or aldehyde, preferably a compound of formula (VIIa), (VIIIa) or (IXa) or stereoisomer thereof 30 wherein 5

[0004] R9a, R9b, R10a, R10b, R11and R12are, independently of each other, selected from H, halogen, CN, C1-C12- alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R9aand R10acombine to form together with the carbon atoms to which they are attached a cyclic group 5 selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Reand m are defined as described herein above; wherein, preferably, in compounds of formula (VIIa) at least one of R9a, R9b, R10aand R10bis not hydrogen and / or one of R9aand R9bin the compounds of formula (IXa) and / or (IX) is hydrogen. 10 In still another aspect, the present invention relates to a process for the production of (1) compounds of formula (X) or (XI) 15 comprising subjecting a compound of formula (IX) to conditions that cause the elimination of nitrogen (N2), wherein R5, R6, R7and R8are as defined above and R9aand R9bare as defined above; (2) compounds of formula (XII) 20 comprising subjecting a compound of formula (VII) to conditions that cause the elimination of nitrogen (N2), wherein R5, R6, R7and R8are as defined above and R9a, R9b, R10aand R10bare as defined above. 25 In one aspect, the present invention relates to a process for the production of compounds of formula (XIII) or (XIV) comprising reacting a compound of formula (I) or (II) as described above with a diene compound, preferably30 a compound of formula (XIIIa) or stereoisomer thereof 6

[0005] (XIIIa) wherein R13, R14, R15, R16, R17and R18are each independently selected from H, halogen, CN, C1-C12-alkyl, C2-C12- 5 alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, C(O)Re, BRcRd, SnRbRcRd, and SiRbRcRd, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, X is selected from C(Rx)2, C=C(Rx)2, C(O), O, S, and NRa; Y is a bond or selected from C(Ry)2, C(O); 10 each Z is selected from C(Rz)2; Rais selected from S(O)mRe, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rb, Rc, Rd, and Reare each independently selected from H, C1-C12-alkyl, C3-C12-cycloalkyl, C2-C12-alkenyl,15 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; each Rx, Ryand Rzis independently selected from H, halogen, CN, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are20 unsubstituted or substituted, or one Rxand one Ryand / or one Rxand one Rzand / or two Rzmay combine to form together with the carbon atom to which they are attached a cyclic group selected from 3 to 12-membered cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, 25 one Ryand one Ra, or one Rzand one Ra, or two Ramay combine to form together with the carbon and / or nitrogen atom(s) to which they are attached a cyclic group selected from 5 to 16-membered hetaryl and 5 to 16-membered heterocyclyl, wherein heterocyclyl and hetaryl are unsubstituted or substituted; m is 1 or 2; and n is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1 or 2, more preferably 0 or 1. 30 In various embodiments of the processes as described above for the production of any one of compounds (V) to (XIV), wherein any one of the following compounds is produced 7 5

[0006] 10 5 10 In still another aspect, the present invention relates to the use of a compound of formula (I) or (II) according to the invention for transfer of a carbon atom or a CN2 group into an organic substrate comprising a pi15 electron system, preferably an organic substrate comprising a carbon-carbon double bond (C(sp2)-C(sp2) 11 bond), more preferably for introducing a single C(sp3) atom into said organic system to create a carbon spiro center. In various embodiments of the processes and the use as described above, the compound of formula (I) or 5(II) is generated in situ.In a further aspect, the present invention relates to compounds of formula (XIII) (XIII) 10 wherein R13, R14, R15, R16, R17and R18are each independently selected from H, halogen, CN, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, 15 X is selected from C(Rx)2, C(O), O, S, and NRa; Y is a bond or selected from C(Ry)2 or C(O); Z is selected from C(Rz)2; Rais selected from S(O)mRe, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are20 unsubstituted or substituted; Rb, Rc, Rd, and Reare each independently selected from H, C1-C12-alkyl, C3-C12-cycloalkyl, C2-C12-alkenyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; each Rx, Ryand Rzis independently selected from H, halogen, CN, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-25 membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, or one Rxand one Ryand / or one Rxand one Rzand / or two Rzmay combine to form together with the carbon atom to which they are attached a cyclic group selected from 3 to 12-membered cycloalkyl, 5 to 16-30 membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, one Ryand one Ra, or one Rzand one Ra, or two Ramay combine to form together with the carbon and / or nitrogen atom(s) to which they are attached a cyclic group selected from 5 to 16-membered hetaryl and 5 to 16-membered heterocyclyl, wherein heterocyclyl and hetaryl are unsubstituted or substituted; 35 m is 1 or 2; and n is 0, 1, 23, 4, 5, or 6, preferably 0, 1 or 2, more preferably 0 or 1, with the proviso that at least one of R13and R14is not hydrogen and wherein compounds where one of R13and R14 is hydrogen and the other is methyl or ethyl or both of R13 and R14 are methyl are excluded. 12 In various embodiments of compounds of formula (XIII) (1) R15and R16are hydrogen; (2) R13and R14are selected from CN, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- 5 membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re,wherein aryl and hetaryl are unsubstituted or substituted; (3) one of X and Y is C(O), O, S, or NRa and the other is C(Rx)2 or C(Ry)2;(4) n is 0 or 1; and / or (5) n is 0 and one Rxand one Rycombine to form together with the carbon atoms to which they are10 attached a phenyl ring, which is unsubstituted or substituted. In still another aspect, the present invention relates to a compound of formula (VI) wherein 15 R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, 20 wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Re, and m are as defined above, wherein, preferably, at least one of R5, R6, R7and R8is not hydrogen. In a further aspect, the present invention relates to a compound of formula (VII), (VIII), (IX), (X), (XI) or25 (XII) 30 13 wherein R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or 5 R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein, preferably, at least one of R5, R6, R7and R8is not hydrogen; R9, R10, R11and R12are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered10 heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R9and R10combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Re, and m are as defined above. 15 Detailed description Unless otherwise indicated, all terms used therein have their common and scientifically accepted meaning. Depending on the substitution pattern, the compounds according to the invention may have one or more20 centers of chirality, in which case they can be present as mixtures of enantiomers or diastereomers. The invention provides both the single pure enantiomers or pure diastereomers of the compounds according to the invention, and their mixtures. Compounds according to the invention also include all possible geometrical stereoisomers (cis / trans isomers) and mixtures thereof. Cis / trans isomers may occur in case of an alkene, carbon-nitrogen double-bond or amide group. Specifically, if the formulae disclosed herein25 show one of the cis and trans isomers, for example the starting compounds having a C-C double bond, it shall be understood that the respective other isomer is also encompassed by the present invention. In other words, if for example only the cis isomer is shown it is understood that it is also possible to use the trans isomer instead, unless the chemistry does not allow it, of which the skilled person would be readily aware. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the30 latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis / trans isomers). The present invention relates to every possible stereoisomer of the compounds disclosed herein, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof. Also encompassed are salts of the compounds of the present invention, if the compound is able to form such a salt. They can be formed by any routine method known in the art, e.g. by reacting the compound with an35 acid of the anion in question if the compound has a basic functionality or by reacting an acidic compound with a suitable base. The organic moieties mentioned herein in the definitions of the variables are - like the term halogen - collective terms for individual listings of the individual members. The prefix Cn-Cm indicates in each case40 the possible number of carbon atoms in the group. The same applies to the term x- to y-membered, in 14 which x and y indicate the minimum and maximum of members with all other integers between x and y being included as well. The term “partially or fully substituted” means that in general the group is substituted with same or different 5 radicals. “Partially substituted” in this context means that not all possible positions are substituted, i.e. typically not all H atoms are replaced by non-H atoms or groups. In contrast, “fully substituted” means that all possible positions are substituted, i.e. typically all H atoms are replaced by non-H atoms or groups. The term “halogen” means in each case fluorine, bromine, chlorine, or iodine, in particular fluorine, chlorine,10 or bromine. The term "alkyl" as used herein means in each case a straight-chain or branched alkyl group having usually from 1 to 12 carbon atoms, frequently from 1 to 10 or from 1 to 6 carbon atoms, such as 1 to 4 carbon atoms or from 1 to 3 carbon atoms. Examples of an alkyl group are methyl (Me), ethyl (Et), n-propyl (n-Pr),15 iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl. 20 The term "alkoxy" as used herein means in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 12 carbon atoms, frequently from 1 to 10 or 1 to 6 carbon atoms, such as 1 to 4 carbon atoms. Examples of alkoxy group include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like. 25 The term "alkenyl" as used herein means in each case a (singly) unsaturated hydrocarbon radical having usually 2 to 12, frequently 2 to 10 or 2 to 6, such as 2 to 4 carbon atoms, e.g. vinyl, allyl (2-propen-1-yl), 1- propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3- penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en-1-yl and the like. 30 The term "cycloalkyl" as used herein means in each case a mono-, bi- or polycyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl (cC3H5), cyclobutyl (cC4H7), cyclopentyl (cC5H9), cyclohexyl (cC6H11), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Similarly, “cycloalkenyl”, as used herein, relates to the same type of35 groups that comprise at least one C-C double bond between ring carbon atoms. The term “carbocycle” or “carbocyclyl” includes in general a 3- to 16-membered, preferably a 3- to 12- membered, or 3- to 10-membered, or 3- to 8-membered, or a 5- to 8-membered, more preferably a 5- or 6- membered mono-, bi- or polycyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more40 preferably 5 or 6 carbon atoms. Preferably, the term “carbocycle” covers cycloalkyl and cycloalkenyl groups as defined herein above. 15 The term “heterocycle” or "heterocyclyl" includes in general 3- to 16-membered, preferably 3- to 12- membered, or 3- to 10-membered, or 5- to 6-membered, in particular 6-membered mono-, bi- or polycyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1, 2, 3, 4 or 5, 5 preferably 1, 2 or 3 heteroatoms selected from N, O, and S, wherein S-atoms as ring members may be present as S, SO, or SO2, and optionally one or two groups C(O) as ring members. Examples of 5- or 6- membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-10 oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxo- dihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S- dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl,15 thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl, N-maleimidyl, 3-maleimidyl, and the like. The term "hetaryl" includes mono-, bi- or polycyclic 5- to 16-membered, for example 5- to 14-membered,20 5- to 12-membered, or 5- to 10-membered, or 5- to 6-membered heteroaromatic radicals comprising as ring members 1, 2, 3 or 4 heteroatoms selected from N, O, and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e.3- or 4-pyridazinyl, thienyl, i.e.2- or 3-thienyl, furyl, i.e.2-or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e.2-, 3- or 5-oxazolyl, isoxazolyl, i.e.3-, 4- or 5-isoxazolyl, thiazolyl, i.e.2-, 3- or25 5-thiazolyl, isothiazolyl, i.e.3-, 4- or 5-isothiazolyl, pyrazolyl, i.e.1-, 3-, 4- or 5-pyrazolyl, i.e.1-, 2-, 4- or 5- imidazolyl, oxadiazolyl, e.g. 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4- oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl, e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, e.g.1H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol- 3-yl, 1H-, 2H-, or 4H-1,2,4-triazolyl and tetrazolyl, i.e.1H- or 2H-tetrazolyl. The term "hetaryl" also includes30 bicyclic 8 to 10-membered heteroaromatic radicals comprising as ring members 1, 2 or 3 heteroatoms selected from N, O, and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical. Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl,35 isochinolinyl, purinyl, 1,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. The groups defined herein may be unsubstituted or substituted. If not indicated otherwise, “substituted” as used herein includes partial and full substitution by one or more substituents that may be selected from a given list of possible substituents. 40 16 If alkyl and / or alkenyl groups are indicated as being “substituted” herein, the substituent is preferably selected from any one or more of the substituents selected from halogen, =O (oxo), -CN, -NO2, -SF5, C3- C6-cycloalk(en)yl, C1-C6-alkoxy, C6-C14-aryl, 5 to 16-membered hetaryl or heterocyclyl, comprising 1 to 5 ring heteroatoms selected from O, N and S, S(O)qRi, ORk, NRgRh, C(O)NRgRh, C(O)ORk, C(O)Ri, wherein 5 cycloalk(en)yl, aryl, heterocyclyl and hetaryl groups may be unsubstituted or substituted with any one or more substituents selected from halogen, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-alkoxy, S(O)qRj, ORj, NRRj, C(O)N(Rj)2, C(O)ORj, and C(O)Rj, wherein q is 0, 1, or 2, Rk, Rg, Rh, and Riare each independently selected from H, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-10 cycloalk(en)yl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, alkylcycloalk(en)yl, alkylaryl, alkylhetaryl, alkylheterocyclyl, alkenylcycloalk(en)yl, alkenylaryl, alkenylhetaryl, alkenylheterocyclyl, cycloalk(en)ylalkyl, cycloalk(en)ylalkenyl, cycloalk(en)ylaryl, cycloalk(en)ylhetaryl, cycloalk(en)ylheterocyclyl, arylalkyl, arylalkenyl, arylcycloalk(en)yl, arylhetaryl, arylheterocyclyl, hetarylalkyl, hetarylalkenyl, hetarylcycloalk(en)yl, hetarylaryl, hetarylheterocyclyl,15 heterocyclylalkyl, heterocyclylalkenyl, heterocyclylcycloalk(en)yl, heterocyclylaryl, heterocyclylhetaryl, wherein alkyl, alkenyl, cycloalk(en)yl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted with any one or more substituents selected from halogen, C1-C6-alkoxy, S(O)qRj, ORj, NRRj, C(O)N(Rj)2, C(O)ORj, and C(O)Rj; and each Rjis independently selected from H, unsubstituted C1-C12-alkyl, unsubstituted C3-C12-cycloalk(en)yl,20 unsubstituted 5 to 16-membered aryl, unsubstituted 5 to 16-membered hetaryl, and unsubstituted 5 to 16- membered heterocyclyl. If cycloalk(en)yl, aryl, hetaryl and / or heterocyclyl groups are indicated as being “substituted” herein, the substituent is typically selected from any one or more of the substituents selected from halogen, =O (oxo)25 (only for cycloalk(en)yl and heterocyclyl), -CN, -NO2, -SF5, C1-C12-alkyl, C2-C12-alkenyl, C3-C6- cycloalk(en)yl, C1-C6-alkoxy, C6-C14-aryl, 5 to 16-membered hetaryl or heterocyclyl, comprising 1 to 5 ring heteroatoms selected from O, N and S, alkylcycloalk(en)yl, alkylaryl, alkylhetaryl, alkylheterocyclyl, alkenylcycloalk(en)yl, alkenylaryl, alkenylhetaryl, alkenylheterocyclyl, cycloalk(en)ylalkyl, cycloalk(en)ylalkenyl, cycloalk(en)ylaryl, cycloalk(en)ylhetaryl, cycloalk(en)ylheterocyclyl, arylalkyl,30 arylalkenyl, arylcycloalk(en)yl, arylhetaryl, arylheterocyclyl, hetarylalkyl, hetarylalkenyl, hetarylcycloalk(en)yl, hetarylaryl, hetarylheterocyclyl, heterocyclylalkyl, heterocyclylalkenyl, heterocyclylcycloalk(en)yl, heterocyclylaryl, heterocyclylhetaryl, S(O)qRi, ORk, NRgRh, C(O)NRgRh, C(O)ORk, C(O)Ri, wherein substituent alkyl, alkenyl, cycloalk(en)yl, aryl, heterocyclyl and hetaryl groups may be unsubstituted or substituted with any one or more substituents selected from halogen, C1-C6-alkoxy,35 S(O)qRj, ORj, NRRj, C(O)N(Rj)2, C(O)ORj, and C(O)Rj, wherein q is 0, 1, or 2, Rk, Rg, Rh, and Riare each independently selected from H, C1-C12-alkyl, C2-C12-alkenyl, C3-C12- cycloalk(en)yl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, alkylcycloalk(en)yl, alkylaryl, alkylhetaryl, alkylheterocyclyl, alkenylcycloalk(en)yl, alkenylaryl,40 alkenylhetaryl, alkenylheterocyclyl, cycloalk(en)ylalkyl, cycloalk(en)ylalkenyl, cycloalk(en)ylaryl, cycloalk(en)ylhetaryl, cycloalk(en)ylheterocyclyl, arylalkyl, arylalkenyl, arylcycloalk(en)yl, arylhetaryl, 17 arylheterocyclyl, hetarylalkyl, hetarylalkenyl, hetarylcycloalk(en)yl, hetarylaryl, hetarylheterocyclyl, heterocyclylalkyl, heterocyclylalkenyl, heterocyclylcycloalk(en)yl, heterocyclylaryl, heterocyclylhetaryl, wherein alkyl, alkenyl, cycloalk(en)yl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted with any one or more substituents selected from halogen, C1-C6-alkoxy, S(O)qRj, ORj, NRRj, C(O)N(Rj)2, 5 C(O)ORj, and C(O)Rj; and each Rjis independently selected from H, unsubstituted C1-C12-alkyl, unsubstituted C3-C12-cycloalk(en)yl, unsubstituted 5 to 16-membered aryl, unsubstituted 5 to 16-membered hetaryl, and unsubstituted 5 to 16- membered heterocyclyl. 10 In these embodiments, in alkylcycloalk(en)yl, alkylaryl, alkylhetaryl, alkylheterocyclyl, alkenylcycloalk(en)yl, alkenylaryl, alkenylhetaryl, alkenylheterocyclyl, cycloalk(en)ylalkyl, cycloalk(en)ylalkenyl, cycloalk(en)ylaryl, cycloalk(en)ylhetaryl, cycloalk(en)ylheterocyclyl, arylalkyl, arylalkenyl, arylcycloalk(en)yl, arylhetaryl, arylheterocyclyl, hetarylalkyl, hetarylalkenyl, hetarylcycloalk(en)yl, hetarylaryl, hetarylheterocyclyl, heterocyclylalkyl, heterocyclylalkenyl, heterocyclylcycloalk(en)yl,15 heterocyclylaryl, heterocyclylhetaryl, the respective groups are preferably C1-C12-alkyl, C2-C12-alkenyl, C3- C12-cycloalk(en)yl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl and may each be substituted as defined above, for example substituted with any one or more substituents selected from halogen, C1-C6-alkoxy, S(O)qRj, ORj, NRRj, C(O)N(Rj)2, C(O)ORj, and C(O)Rjwith each Rjbeing independently selected from H, unsubstituted C1-C12-alkyl, unsubstituted C3-C12-cycloalk(en)yl,20 unsubstituted 5 to 16-membered aryl, unsubstituted 5 to 16-membered hetaryl, and unsubstituted 5 to 16- membered heterocyclyl . In structures such as the following: it is understood that the each of the corners of the ring structure as well as the crossing25 point represent carbon atoms, with the point where the 4 ring bonds connect being the spiro carbon atom (introduced according to the methods and techniques described herein). In a first aspect, the present invention is directed to compound of formula (I) or (II) 30 (I) (II)wherein in formula (I) or (II), R1and R2are independently of each other selected from alkyl, cycloalkyl, heterocyclyl, aryl, hetaryl, NRcRd, preferably C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- membered heterocyclyl, NRcRd, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted35 or substituted; or R1and R2combine to form together with the sulfur atom to which they are attached a 5 to 16-membered hetaryl or heterocyclyl ring that is unsubstituted or substituted; 18 Rsis selected from O and NRa, wherein each Rais independently selected from S(O)mRe, C1-C12-alkyl, C3- C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rc, Rd, and Reare each independently selected from C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered 5 aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; and m is 1 or 2. In various embodiments, R1and R2may be identical. In various other embodiments, R1and R2are different. 10 In various embodiments of the compounds of formula (I) and (II), R1and / or R2, preferably both, are selected from unsubstituted or substituted alkyl, cycloalkyl, heterocyclyl, aryl and hetaryl. In various embodiments, alkyl is C1-C6 alkyl, which may be substituted or unsubstituted, such as tert-butyl. In various embodiments, cycloalkyl, is C3-C12 cycloalkyl, which may be substituted or unsubstituted, such as adamantyl. In various15 embodiments, aryl is C6-C12 aryl, such as unsubstituted or substituted phenyl. In various embodiments, hetaryl / heterocyclyl is 5- to 12-membered hetaryl / heterocyclyl with 1 to 3 heteroatoms selected from S, O and N, preferably from O and N, such as unsubstituted or substituted pyrrolyl and / or unsubstituted or substituted pyridinyl. 20 In various embodiments, R1and R2combine to form together with the sulfur atom to which they are attached a 5 to 16-membered hetaryl or heterocyclyl ring that is monocyclic, bicyclic or tricyclic and is unsubstituted or substituted. Said ring may, for example, be selected from tetrahydrothiophene, thianthrene, dibenzothiophene, phenothiazine, and tetrahydro-4H,9H-thieno[2,3-d:4,5-d']bis([1,3]dioxine, all of which may be unsubstituted or substituted. 25 In various embodiments, the compound of formula (I) is thus selected from any one of the following 30 19 I-5 I-6 I-7 I-85 In various embodiments, the compound of formula (II) is a compound of formula (IIa): 10 wherein Rfis C1-C6-alkyl, C3-C6-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, or 5 to 16- membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted. 15 The inventors have surprisingly found that the compounds of formula (I) and (II) and the concrete compounds described above advantageously combine the properties of sulfur ylides and diazo compounds and can be used for novel C-atom transfer reactions which accomplish the single-step transfer of a C(sp3)- atom into an acceptor structure, as described herein below. This makes them an ideal reagent for the creation of spiro-C-centers, particularly for the direct formation of spiro[2.2]pentanes in which four new C‒20 C bonds are created, with these compounds not being easily accessible via different and known synthetic routes. The compounds of formula (I) and (II) are thus single-step C(sp3)-atom transfer reagents that allow the construction of C(sp3)-rich, three-dimensional and rigid spirocyclic scaffolds from readily available two- dimensional feedstock molecules. 25 The diazo sulfur ylides of formulae (I) and (II) can be obtained by using phosphorus ylides of formula (III) or (IV), as defined herein below, as starting molecules. These phosphorus ylides can themselves be obtained by reacting a precursor, such as hexaphenylcarbodiphosphorane, with nitrous oxide to generate the desired phosphorus ylide together with triphenylphosphine oxide via a Ph3P / N2 exchange reaction. 20 The present invention thus also features a method or process for producing the compounds of formula (I) or (II). Specifically, said process for producing a compound according to formula (I) or (II) may comprise reacting a compound of formula (III) or (IV) 5(III) (IV)wherein each Rpis independently an organic moiety, preferably selected from alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, preferably phenyl or alkyl, or wherein two or three Rpcombine to form together with the P atom to which they are attached a 5 to 16-membered hetaryl or heterocyclyl ring that is monocyclic, bicyclic or tricyclic10 and is unsubstituted or substituted, with nitrous oxide (N2O) to produce the compound according to formula (I) or (II). It is understood that using the compounds of formula (III) as starting material, the compounds of formula (I) are obtained; while using the compounds of formula (IV) as starting material, the process yields compounds15 of formula (II). In the compounds of formulae (III) and (IV), all Rpare, in various embodiments, identical, and for example an aryl, heteroaryl, heterocyclyl, cycloalkyl or alkyl group, such as, for example and without limitation, phenyl, in particular unsubstituted phenyl. 20 In other embodiments, the Rpresidues are different. In such embodiments, one may still be selected from those listed above, i.e. an aryl, heteroaryl, heterocyclyl, cycloalkyl or alkyl group, such as, for example and without limitation, phenyl, in particular unsubstituted phenyl, while the other two may combine to form a ring, in particular a heterocyclyl ring that optionally also comprises one or more additional heteroatoms,25 such as N atoms, for example two additional ring atoms. The ring may be a 5-membered heterocyclic ring, for example of the structure -NRf-(CH2)2-3-NRf-, wherein each Rfis independently C1-C6-alkyl, C3-C6- cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, or 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, preferably unsubstituted, more preferably unsubstituted alkyl, such as isopropyl. 30 In various embodiments, in the compound of formula (III) or (IV) all Rpare unsubstituted phenyl or one Rpis unsubstituted phenyl and the other two combine to form the group -N(iPr)-CH2-CH2-N(iPr)-, with “iPr” being isopropyl. This is particularly preferred for the compounds of formula (III). Ylides with the described ring structures formed by two Rpgroups are preferred, in particular the specific one disclosed above, since35 it allows the simple separation of the phosphine oxide which is generated in the reaction, for example by washing, while use of other starting compounds make the isolation of the target compound more challenging. 21 In the compounds of formula (III) and (IV) a suitable counterion can be used, including, without limitation, TfO- (triflate; trifluoromethanesulfonate). It is however understood that a variety of other suitable counterions can be used, all of which are readily known to those skilled in the art. 5In the claimed process, the phosphonium salt of formula (III) or (IV) may first be deprotonated with a suitableBronsted base, such as potassium bis(trimethylsilyl)amide (KHMDS), to obtain the mixed P / S-ylide. In the subsequent reaction of the mixed P / S ylide with N2O the compound of formula (I) or (II) is obtained. The deprotonated compound of formula (III) may thus have the following exemplary structure: 10 In various embodiments, in the claimed processes, the reaction is carried out in the presence of a Bronsted base, in particular a strong and, optionally, non-nucleophilic base, such as, without limitation, potassium bis(trimethylsilyl)amide (KHMDS) or LDA. “Strong base”, as used in this context, refers to a base where the15 corresponding acid has a pKa value of 15 or more, for example 20 or more. The reaction may be carried out at low temperatures, such as, for example, -78°C, and up to room temperature (25°C).20 The compounds of formula (I) and (II) may also be created in situ, for example by the described processes,and then directly used for the following reactions. The present invention thus also features the use of the compounds of formula (I) and (II) in a reaction with an olefin / unsaturated compound, such as those of formulae (Va) and (VIa), defined below, to yield25 compounds of formula (VI) and (V). In various embodiments, the invention is thus directed to a process for the production of compounds of formula (VI) 30 comprising reacting a compound of formula (I) or (II) with an olefin, preferably a compound of formula (VIa) or stereoisomer thereof 22 (VIa) wherein R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered 5 heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, Rb, Rc, Rd, and Reare each independently selected from C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered10 aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; and m is 1 or 2. If one of R5and R6is hydrogen and one of R7and R8is hydrogen, the compound of formula (VIa) can be a15 compound of formula (Va) or stereoisomer (such as the trans isomer) thereof wherein R3and R4are defined as R5, R6, R7, R8above, i.e. are independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered20 hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R3and R4combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted. 25 In various embodiments, the compound of formula (Va) has preferably the shown cis stereochemistry. In various embodiments, at least one of R3and R4and / or at least one of R5, R6, R7and R8is not hydrogen. In various embodiments, the compounds of formula (Va) are selected, without limitation, from the following:30 , In various embodiments, the compounds of formula (VIa) are selected, without limitation, from the following: 23 5 The compound of formula (VI) may react further to yield the compound of formula (V), in particular if the compound of formula (VIa) is a compound of formula (Va): (V) Starting from the compounds of formula (VI) in these embodiments the fast 3+2 cycloaddition is followed10 by a slower, 1,3-proton migration / shift and (R1)(R2)S elimination which yields the aromatic pyrazoles of formula (V). The formation of the pyrazoles of formula (V) may further be dependent on the C-H acidity of the carbon atoms bearing the R3and R4groups. If said acidity is too low, the compounds of formula (V) are not formed quantitatively from the compounds of formula (VI). 15 The processes described above yield compounds of formula (V) or (VI) that may be any one of the following

[0007] 24 5,, , 10 In one aspect, the present invention also relates to the compounds of formula (V) and (VI), as defined herein above, and also encompasses all specific examples thereof disclosed herein. The compounds of formula (VI) described herein above may be used in a further reaction with a compound15 having a carbon-carbon double bond or an aldehyde group. These compounds with which the compounds of formula (VI) may be reacted include, but are not limited to, those of formulae (VIIa), (VIIIa) or (IXa) 25 (VIIa) (VIIIa) (IXa)wherein R9a, R9b, R10a, R10b, R11and R12are, independently of each other, selected from H, halogen, CN, C1-C12- 5 alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R9aand R10acombine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and10 wherein Rb, Rc, Rd, Reand m are defined as above; wherein, preferably, in compounds of formula (VIIa) at least one of R9a, R9b, R10aand R10bis not hydrogen. Suitable compounds of formula (VIIa) include, but are not limited to the following:15 . Suitable compounds of formula (IXa) include, but are not limited to the following:20 n can be 1 or more, such 1 to 10. Reaction of the compounds of formula (VI) with those of formula (VIIa), yields compounds of formula (VII) 25 (VII). 26 Examples for compounds of formula (VII) that are obtainable by the described processes include, but are not limited to:5 27 . 5 Reaction of the compounds of formula (VI) with those of formula (VIIIa), yields compounds of formula (VIII) (VIII). Examples for compounds of formula (VIII) that are obtainable by the described processes include, but are10 not limited to: Reaction of the compounds of formula (VI) with those of formula (IXa), yields compounds of formula (IX) 28 Examples for compounds of formula (IX) that are obtainable by the described processes include, but are 5 not limited to: 10 The present invention thus relates to processes for the production of compounds of formula (VII), (VIII) or (IX) 29 comprising reacting a compound of formula (VI) with an olefin, methylenecyclopropane, ketone or aldehyde, preferably a compound of formula (VIIa), (VIIIa) or (IXa) 5 (VIIa) (VIIIa) (IXa)wherein R9a, R9b, R10a, R10b, R11and R12are, independently of each other, selected from H, halogen, CN, C1-C12-10 alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R9aand R10acombine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and15 wherein Rb, Rc, Rd, Reand m are defined as above. In various embodiments, in compounds of formula (VIIa) at least one of R9a, R9b, R10aand R10bis not hydrogen. 20 In various preferred embodiments, one of R9aand R9bin the compounds of formula (IXa) and / or (IX) is hydrogen. In some embodiments, both may be hydrogen. The invention further relates to a process for the production of compounds of formula (X) or (XI) 25 (X) (XI)comprising subjecting a compound of formula (IX) to conditions that cause the elimination of nitrogen (N2). R5, R6, R7, R8, R9aand R9bare as defined herein above. In various embodiments, this is a thermally induced nitrogen elimination. This elimination reaction may be carried out at elevated temperatures such as 60 to 90°C, for example about 80°C, for an extended period of time, such as 6 to 50 hours, for example 10 to 3030 hours, such as about 24 hours. The reaction may be carried out in, for example, C6D6. 30 The compounds of formula (XI) may be generally obtained from the compounds of formula (X) in which at least one of R9aand R9bis not hydrogen by a Meinwald-type rearrangement, where the higher substituted carbon atom migrates. 5 In the compounds of formula (X) and / or (XI) at least one of R9aand R9bmay be hydrogen. In some embodiments both are hydrogen. Examples for compounds of formula (X) that are obtainable by the described processes include, but are not limited to:10 Examples for compounds of formula (XI) that are obtainable by the described processes include, but are not limited to: 15 . The invention further relates to processes for producing compounds of formula (XII) 31 comprising subjecting a compound of formula (VII) to conditions that cause the elimination of nitrogen (N2). In various embodiments, this is a thermally induced nitrogen elimination. This elimination reaction may be 5 carried out at elevated temperatures such as 90°C to 180°C, for example about 130°C to 165 °C, for an extended period of time, such as 2 to 50 hours, for example 3, 5 or 48 hours. The reaction may be carried out in, for example, C6D5Br. Examples for compounds of formula (XII) that are obtainable by the described processes include, but are10 not limited to: 32 , In invention further relaters to a process for the production of compounds of formula (XIII) or (XIV) 5 comprising reacting a compound of formula (I) or (II) as described herein above with a diene compound, preferably a compound of formula (XIIIa) 10 (XIIIa) wherein R13, R14, R15, R16, R17and R18are each independently selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, C(O)Re, BRcRd, SnRbRcRd, and SiRbRcRd, wherein alkyl,15 alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, X is selected from C(Rx)2, C=C(Rx)2, C(O), O, S, and NRa; Y is a bond or selected from C(Ry)2, C(O); each Z is selected from C(Rz)2; Rais selected from S(O)mRe, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered20 hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rb, Rc, Rd, and Reare each independently selected from H, C1-C12-alkyl, C3-C12-cycloalkyl, C2-C12-alkenyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; 33 each Rx, Ryand Rzis independently selected from H, halogen, CN, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, or 5 one Rxand one Ryand / or one Rxand one Rzand / or two Rzmay combine to form together with the carbon atom to which they are attached a cyclic group selected from 3 to 12-membered cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, one Ryand one Ra, or one Rzand one Ra, or two Ramay combine to form together with the carbon and / or10 nitrogen atom(s) to which they are attached a cyclic group selected from 5 to 16-membered hetaryl and 5 to 16-membered heterocyclyl, wherein heterocyclyl and hetaryl are unsubstituted or substituted; m is 1 or 2; and n is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1 or 2, more preferably 0 or 1. 15 In various embodiments, at least one of R13and R14is not hydrogen. In various embodiments, if one of R13and R14is methyl the other is not hydrogen or methyl. In various embodiments, if one of R13and R14is ethyl the other is not hydrogen or methyl or ethyl. In various embodiments, in the groups BRcRd, SnRbRcRd, and SiRbRcRd, Rb, Rcand Rdare not hydrogen. 20 If Y is a bond, this means that the carbon atom bearing R13and X are directly bound to each other. If n is 0, this means that the carbon atom bearing R14and X are directly bound to each other. 25 In various embodiments, the process comprises a first step wherein the compound of formula (I) or (II) as described herein above is reacted with a diene compound, preferably a compound of formula (XIIIa), to produce a compound of formula (XIV). In a second step, this compound of formula (XIV) undergoes a N2 elimination to yield the compound of formula (XIII). Said nitrogen elimination may be carried out at elevated temperatures, as described herein above, or by irradiation, for example with blue light at 370 nm at room30 temperature (20-25°C). The type of elimination reaction used may influence the stereochemistry of the product. The processes may be carried out in a suitable solvent, such as THF. 35 In various embodiments, the process for producing the compounds of formula (XIII) or (XIV) can be carried out as a one pot reaction in which the compounds of formula (I) or (II) are first generated in situ as describedherein above (from the compounds of formulae (II) and / or (IV)) and then directly reacted with a compound of formula (XIIIa) to yield the compounds of formula (XIV) and subsequently of formula (XIII). 40 Examples for compounds of formula (XIII) that are obtainable by the described processes include, but are not limited to: 34 10 Examples for compounds of formula (XIV) that are obtainable by the described processes include, but are not limited to: 35 ,, 5 Examples for compounds of formula (XIIIa) that can be used in the described processes include, but are not limited to: ,, 10 The present invention also features the use of a compound according to formula (I) or (II) as described herein for transfer of a carbon atom or a CN2group into an organic substrate comprising a pi electron system. Said use may be for transfer of a carbon atom or a CN2 group into an organic substrate comprising15 a carbon-carbon double bond (C(sp2)-C(sp2) bond). Said use may also be for introducing a single C(sp3) atom into the organic substrate, as described above, to create a carbon spiro center. As already described herein below for the production of compounds of formula (XIII) or (XIV), in all processes and uses described herein, the compound of formula (I) or (II) may be generated in situ, typically20 from the compounds of formula (III) or (IV), as described herein above. All the processes described herein may thus be carried out as one-pot reactions. The present invention also relates to the compounds of formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII) and (XIV) obtainable by the described processes. Furthermore, the invention also encompasses all 36 compounds of formulae (VI), (VII), (VIII), (IX), (X); (XI), (XII), (XIII) and (XIV) described herein in relation to the inventive processes per se.The invention is particularly also directed to compounds of formula (XIII) 5 wherein R13, R14, R15, R16, R17and R18are each independently selected from H, halogen, CN, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered10 hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, X is selected from C(Rx)2, C(O), O, S, and NRa; Y is a bond or selected from C(Ry)2 or C(O); Z is selected from C(Rz)2; 15 Rais selected from S(O)mRe, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rb, Rc, Rd, and Reare each independently selected from H, C1-C12-alkyl, C3-C12-cycloalkyl, C2-C12-alkenyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl,20 cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; each Rx, Ryand Rzis independently selected from H, halogen, CN, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, or 25 one Rxand one Ry, or one Rxand one Rzmay combine to form together with the carbon atom to which they are attached a cyclic group selected from 3 to 12-membered cycloalkyl, 5 to 16-membered aryl, 5 to 16- membered hetaryl, and 5 to 16-membered heterocyclyl, wherein cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, or one Rxand one Ra, or one Ryand one Ra, or one Rzand one Ra, or two Ramay combine to form together30 with the carbon and / or nitrogen atom(s) to which they are attached a cyclic group selected from 5 to 16- membered hetaryl and 5 to 16-membered heterocyclyl, wherein heterocyclyl and hetaryl are unsubstituted or substituted; m is 1 or 2; and n is 0, 1, 23, 4, 5, or 6, preferably 0, 1 or 2, more preferably 0 or 1. 35 In these compounds, which became accessible by the newly developed synthetic processes, at least one of R13and R14is not hydrogen. Compounds where one of R13and R14is hydrogen and the other is methyl or ethyl or both of R13 and R14 are methyl are excluded. It has been advantageously found that the new 37 synthetic processes allow synthesis of compounds where R13and / or R14are a variety of groups other than H, methyl or ethyl. The invention thus also covers embodiments, wherein R13and / or R14are as defined above with the exception of H, methyl and ethyl. 5 These compounds of formula (XIII) have particular use as intermediates or starting compounds for the synthesis of novel classes of biologically active compounds, in particular pharmaceuticals. In the compounds of formula (XIII), R15and R16may both be hydrogen. 10 In the compounds of formula (XIII), R13and R14may be selected from CN, 5 to 16-membered aryl, 5 to 16- membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re,wherein aryl and hetaryl are unsubstituted or substituted. In the compounds of formula (XIII), X may be C(O), O, S, or NRaand Y may be C(Ry)2. 15 In the compounds of formula (XIII), Y may be C(O) and X may be C(Rx)2. In the compounds of formula (XIII), n may be 0 or 1. 20 In the compounds of formula (XIII), n may be 0 and one Rxand one Rymay combine to form together with the carbon atoms to which they are attached a phenyl ring, which is unsubstituted or substituted. Specific examples of compounds of formula (XIII) encompassed by the present invention are those disclosed above in relation to the processes of the invention. 25 The invention is further directed to compounds of formula (VI) wherein R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12-30 alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and35 wherein Rb, Rc, Rd, Re, and m are defined as herein above. In such compounds of formula (VI), at least one of R5, R6, R7and R8may not be hydrogen. Stll further, the invention relates to compounds of formula (VII), (VIII), (IX), (X), (XI) or (XII) 38 5 R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered10 heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, R9, R10, R11and R12are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12- alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered15 heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R9and R10combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Re, and m are defined as described herein above. 20 In such compounds, at least one of R5, R6, R7and R8may not be hydrogen. Specific examples of compounds of formulae (VI), (VII), (VIII), (IX), (X), (XI), or (XII), encompassed by the present invention are those disclosed above in relation to the processes of the invention. 25 All embodiments disclosed herein in relation to the inventive processes are similarly applicable to the described uses and compounds and vice versa. The present invention is further illustrated by the following non-limiting examples. 30 Examples General information 39 The reaction and handling of air-sensitive compounds were carried out under N2 atmosphere using a high- vacuum line, standard Schlenk techniques, or a glovebox, as well as dry and oxygen-free solvents.1H, 13Cand 31P nuclear magnetic resonance (NMR) spectra were recorded on a Bruker AV 500 Avance NEO,Bruker AV 400 Avance III HD NanoBay, AV 600 Avance III HD and AV 700 Avance III HD spectrometer at 5 298 K unless otherwise noted. NMR chemical shifts (δ) in C6D6, CDCl3, CD2Cl2, THF-d8, C6D5Br or CD3CN are referenced to their solvent signals [C6D6, 7.16 (1H NMR), 128.06 (13C NMR); CD3CN, 1.94 (1H NMR), 118.26 (13C NMR), CDCl37.26 (1H NMR), 77.16 (13C NMR), CD2Cl2, 5.32 (1H NMR), 53.84 (13C NMR), THF-d8, 3.58 (1H NMR), 67.21 (13C NMR), C6D5Br, 6.94 (1H NMR), 122.35 (13C NMR)]. 31P NMR chemicalshifts are relative to 85% aqueous H3PO4 in ppm. Data are reported as follows: chemical shift, multiplicity10 (s = singlet, d = doublet, t = triplet, sep = septet, brs = broad singlet, brd = broad doublet, m = multiplet), coupling constant in Hertz (Hz), and an integration value. High resolution MS (EI): Finnigan MAT 8200 (70 eV), ESIMS: Finnigan MAT 95, accurate mass determinations: Bruker APEX III FT-MS (7 T magnet) and LTQ-Orbitrap-XL (Thermo Scientific) equipped with a heated electrospray ionization source (HESI). Flash chromatography was performed with Merck 60 silica gel (40-63 μm). Thin-layer chromatography (TLC)15 analysis was performed using Merck silica gel 60 F254 TLC plates and visualized by UV irradiation and / or ceric ammonium molybdate, KMnO4 or p-anisaldehyde. The reactions were performed under dry argon ornitrogen atmosphere unless otherwise noted. IR-ATR measurements (diamond) were performed in reflection mode on a Bruker Alpha II inside a glovebox, wavenumbers in cm−1. Melting points were measured with a Büchi M-560 apparatus. N2O was directly used from the gas bottle (quality 5.0 obtained20 from Messer). Materials: compound 1b (protonated 2b), 2b, 2b-13C, 12a, 12b, 12c, 12d, 12e, 12f, 12h were prepared asdescribed in the literature (Dellus et al., Angew. Chem. Int. Ed.49, 6798-6801 (2010); Pratsch & Overman,J. Org. Chem. 80, 11388−11397 (2015); Maraswami et al., ACS Catal.11, 11494−11500 (2021); Stetter &25 Kuhlmann, Synthesis 1, 29−30 (1979); Drewes et al., Synth. Commun., 17, 291−298 (1987); Mangelinckxet al. Tetrahedron Lett. 49, 6896–6900 (2008)). All other reagents were commercially available and usedas received. In all racemic compounds the symbol “(±)” was omitted for the sake of clarity. 30

[0008] 40 Synthesis of compound 1a 5 To a suspension of [Ph2SCH3][OTf] (1.40 g, 4.0 mmol) in THF (10 mL) was added dropwise n-BuLi(2.75 mL, 1.6 M solution in hexanes, 4.4 mmol) at -78 °C. After stirring at -78 oC for 15 min, a cold (-78 oC)solution of Ph3PCl2 (0.67 g, 2.0 mmol) in THF (10 mL) was quickly added. The mixture was then slowly warmed up to rt. The reaction was stirred at room temperature for 30 min. All the volatiles were removed10 under vacuum. A suspension was obtained after adding CH2Cl2 (10 mL) to the residue. The suspension was filtered by a filter cannula to obtain a clear CH2Cl2 solution. The volatiles were removed to a volume of ca.2 mL. Et2O (20 mL) was added into the solution with continuous stirring, during the stirring, a colorless solid formed, which was collected by filtration and washed with Et2O (2×3 mL) to give compound 1a (0.62g, 1.02 mmol, 51%). 15 Characterization data of compound 1a: 1H NMR (500 MHz, 298 K, CD3CN): δ = [7.75 (4H), 7.61 (21H)](each m, Ph), 3.12 (d, 2JPH = 16.4 Hz, CH).13C{1H} NMR (125 MHz, 298 K, CD3CN): δ = 138.3 (d, J = 4.5 Hz), 134.8 (d, J = 3.0 Hz), 134.2 (d, J = 10.5Hz), 133.0, 131.4, 130.6 (d, J = 12.5 Hz), 128.4, 126.0 (d, J = 93.3 Hz), 10.2 (d, 1JPC = 127.9 Hz, CH).2031P NMR (195 MHz, 298 K, CD3CN): δ = 24.6 (ν1 / 2 ~ 2 Hz). IR (ATR) [cm-1]: ṽ = 3058, 1585, 1481, 1439, 1322, 1287, 1255, 1243, 1224, 1192, 1179, 1166, 1154, 1104,1055, 1049, 1038, 998, 960, 847, 824, 759, 746, 719, 688, 642, 598, 573, 539, 513, 501, 441, 409. HR-MS-ESI(+) calc. C31H26PS+ [M]+ 461.1488, found 461.1496.25 Synthesis of compound 2a A solution of potassium bis(trimethylsilyl)amide (KHMDS) (43.8 mg, 0.22 mmol) in THF (5.0 mL) was added dropwise to a solution of compound 1a (122.0 mg, 0.2 mmol) in THF (10 mL) at -78 oC for 10 min. The30 reaction mixture was stirring at room temperature for one hour. All the volatiles were removed under reduced pressure, the remaining residue was extracted with Et2O (3×5 mL). The solution was concentrated to a volume of solution ca.2 mL. n-Pentane (5 mL) was added to the remaining solution and kept at -40 oC.During this time a yellow solid formed, which was collected by filtration and washed with cold n-pentane(3×1 mL) to give the desired compound 2a (52.4 mg, 0.11 mmol, 57%).35 41 Characterization data of compound 2a: 1H NMR (500 MHz, 298 K, THF-d8): δ = [7.89 (4H, o-), 7.28 (4H, m-), 7.21 (2H, p-)](each m, Ph-S), [7.66(6H, o-), 7.35 (3H, p-), 7.30 (6H, m-)](each m, Ph-P).13C{1H} NMR (125 MHz, 298 K, THF-d8): δ = 151.1 (d, 3JPC = 20.0 Hz, i-Ph-S), 136.4 (d, 1JPC = 136.4 Hz, i-5 Ph-P), 133.1 (d, 2JPC = 8.3 Hz, o-Ph-P), 130.2 (d, 4JPC = 2.5 Hz, p-Ph-P), 128.94 (p-Ph-S), 128.86 (m-Ph-S), 128.3 (d, 3JPC = 10.3 Hz, m-Ph-P), 126.5 (o-Ph-S), 22.9 (d, 1JPC= 15.1 Hz, P=C=S).31P NMR (195 MHz, 298 K, THF-d8): δ = 8.1 (ν1 / 2 ~ 2 Hz). IR (ATR) [cm-1]: ṽ = 3051, 2058, 1954, 1578, 1472, 1434, 1302, 1234, 1177, 1098, 1046, 1019, 995, 917,885, 825, 738, 689, 630, 534, 511, 499. 10 Synthesis of compound 3 Asolution of compound 2b (224 mg, 0.5 mmol) was dissolved in THF (10 mL) and degassed by freeze-15 pump-thaw cycles twice at -78 °C. Then the mixture was exposed to a N2O atmosphere (1.0 bar) at -78 oC(Note: N2O was directly used from the gas bottle; quality 5.0 obtained from Messer). The reaction mixture was gradually raised to room temperature and stirring was continued for one hour at this temperature. (Caution: the actual pressure in the flask at room temperature is higher; use pressure glassware and explosion shield). The volatiles were removed to a volume of solution of ca.1 mL. n-Pentane (10 mL) was20 added into the solution with continuous stirring, during this time a yellow solid formed, which was collected by filtration and washed with cold n-pentane (3×1 mL) to give the desired diazo sulfur ylide 3 (94.9 mg, 0.42mmol, 84%). Crystals of diazo sulfur ylide 3 suitable for X-ray diffraction were obtained from a solution ofthe yellow solid in THF and n-pentane (ratio: 1:2) at -40 oC.25 For isolation of compound 4b: All volatiles of the above obtained filtrate were removed under vacuum andthe remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 2:1) to give compound 4b (121.0 mg, 0.46 mmol, 91%) as a colorless oil.Characterization data of compound 3:30 m.p.80 oC (decompostion).1H NMR (500 MHz, 213 K, THF-d8): δ = 7.86 (m, o-Ph, 4H), 7.54 (m, m, p-Ph, 6H).1H NMR (500 MHz, 298 K, C6D6): δ = 7.40 (m, o-Ph, 4H), 6.82 (m, m, p-Ph, 6H).13C{1H} NMR (125 MHz, 213 K, THF-d8): δ = 138.4 (i-Ph), 132.1 (p-Ph), 130.5 (m-Ph), 128.1 (o-Ph), 21.3(CN2).35 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 137.9 (i-Ph), 130.9 (p-Ph), 129.6 (m-Ph), 127.8 (o-Ph), 23.7(CN2). 42 15N NMR (61 MHz, 233 K, THF-d8): δ = 274.4, 266.8.IR (ATR) [cm-1]: ṽ = 3055, 1963 (CN2), 1579, 1474, 1442, 1304, 1213, 1066, 1022, 996, 838, 741, 688,563, 513, 470. 5 Characterization data of compound 4b: [Comment: the NMR data for the obtained colorless oil corresponded to the data reported in the literature.24] 1H NMR (500 MHz, 298 K, CDCl3): δ = 7.80 (m, 2H, o-Ph), 7.45 (m, 1H, p-Ph), 7.40 (m, 2H, m-Ph), 7.36(m, 2H, CHiPr), [7.36, 3.21](each m, each 2H, CH2), [1.15, 0.94](each d, each 3JHH = 6.6 Hz, each 6H,CH3iPr).10 13C{1H} NMR (125 MHz, 298 K, CDCl3): δ = 134.2 (d, 1JPC = 156.8 Hz, i-Ph), 133.0 (d, 2JPC = 9.9 Hz, o-Ph),131.2 (d, 4JPC = 3.0 Hz, p-Ph), 128.2 (d, 3JPC = 13.5 Hz, m-Ph), 44.8 (d, 2JPC = 6.2 Hz, CHiPr), 40.1 (d, 2JPC= 9.7 Hz, CH2), [21.7 (d, 3JPC = 2.4 Hz), 20.7 (d, 3JPC = 4.3 Hz)](CH3iPr).31P NMR (195 MHz, 298 K, CDCl3): δ = 24.4 (ν1 / 2 ~ 3 Hz).15 Synthesis of 13C labeled compound 3-13C Compound 2b-13C (112.4 mg, 0.25 mmol) was dissolved in THF (5 mL) and degassed by freeze-pump-thaw cycles twice at -78 °C. Then the mixture was exposed to a N2O atmosphere (1.0 bar) at -78 oC (Note:20 N2O was directly used from the gas bottle; quality 5.0 obtained from Messer). The reaction mixture was gradually raised to room temperature and stirring was continued for 1 h at this temperature. (Caution: the actual pressure in the flask at room temperature is higher; use pressure glassware and explosion shield). The volatiles were concentrated up to ca. 1 mL of solution. n-Pentane (10 mL) was added to the solutionwith continuous stirring, during this time a yellow solid formed, which was collected by filtration and washed25 with cold n-pentane (3×1 mL) to give compound 3-13C (47.2 mg, 0.21 mmol, 83%).Characterization data of compound 3-13C: 1H NMR (500 MHz, 213 K, THF-d8): δ = 7.86 (m, o-Ph, 4H), 7.54 (m, m, p-Ph, 6H).13C{1H} NMR (125 MHz, 213 K, THF-d8): δ = 138.4 (d, 2JCC = 10.1 Hz, i-Ph), 132.1 (p-Ph), 130.5 (m-Ph),30 128.1 (d, 3JCC = 2.7 Hz, o-Ph), 21.3 (CN2). 43 Synthesis of compound 5a A solution of N-methylmaleimide (11.1 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of 5compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 15 min. All thevolatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution withcontinuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5a (30.7 mg, 0.091 mmol, 91%). Crystals of compound 5asuitable for X-ray diffraction were obtained from a solution of the light-yellow solid in THF and n-pentane10 (ratio: 1:3) at -40 oC.Characterization data of compound 5a: 1H NMR (500 MHz, 253 K, THF-d8): δ = [7.84 (2H, o-Ph), 7.58 (5H), 7.51 (3H)](each m, Ph), 5.27 (d, 3JHH= 11.0 Hz, 1H, CH-N), 3.59 (m, 1H, CH-CS), 2.80 (s, 3H, Me).15 13C{1H} NMR (125 MHz, 253 K, THF-d8): δ = 177.5 (C=Ob), 174.0 (C=Oa), [136.1, 133.8 (br), 132.4, 131.6,130.8, 130.5, 130.2, 128.6](Ph), 88.3 (br, S=C), 84.1 (CH-N), 45.5 (CH-CS), 24.3 (Me). IR (ATR) [cm-1]: ṽ = 1774, 1696, 1475, 1442, 1378, 1278, 1207, 1176, 1109, 1063, 998, 960, 911, 748,689, 558, 511, 466. HR-MS-ESI(+) calc. C18H16N3O2S+ [M+H]+ 338.0958, found 338.0968.20 Synthesis of compound 5b A solution of di-tert-butyl 2-methylene malonate (22.8 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 15min. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the residue25 with continuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5b (41.8 mg, 0.092 mmol, 92%).Characterization data of compound 5b: 1H NMR (500 MHz, 298 K, C6D6): δ = 7.05 (m, 4H, o-Ph), 6.86 (m, 6H, m, p-Ph), 3.20 (s, 2H, CH2), 1.45 (s,30 18H, tBu).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 169.2 (C=O), 133.4 (i-Ph), 130.9 (p-Ph), 129.9 (m-Ph), 128.5(o-Ph), [93.0, 89.5](C-N, C=S), [81.0, 28.0](tBu), 31.7 (CH2). 44 IR (ATR) [cm-1]: ṽ = 2977, 2932, 1718, 1580, 1475, 1443, 1392, 1367, 1335, 1290, 1247, 1170, 1127, 1060,1024, 998, 882, 847, 744, 689, 614, 551, 513, 486, 464. HR-MS-ESI(+) calc. C25H31N2O4S+ [M+H]+ 455.2000, found 455.2012.5 Synthesis of compound 5c A solution of methyl methacrylate (10.0 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 15 min. All thevolatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution with10 continuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5c (30.0 mg, 0.092 mmol, 92%).Characterization data of compound 5c: 1H NMR (500 MHz, 298 K, THF-d8): δ = [7.53, 7.52](each m, each 5H, Ph), 3.63 (s, 3H, OCH3), [2.97,15 1.98](each d, each 2JHH = 12.8 Hz, each 1H, CH2), 1.30 (s, 3H, Me).13C{1H} NMR (125 MHz, 298 K, THF-d8): δ = 173.8 (C=O), [135.2, 134.9, 131.7, 131.4, 130.6, 130.4, 129.4,128.9](Ph), 88.8 (C-N), 84.5 (S=C), 51.7 (OCH3), 34.4 (CH2), 22.8 (Me). IR (ATR) [cm-1]: ṽ = 3056, 2949, 2926, 2855, 2154, 2017, 1966, 1726, 1579, 1475, 1442, 1346, 1288, 1243,1189, 1159, 1116, 1070, 1022, 997, 924, 883, 838, 746, 689, 616, 560, 513, 484, 451.20 HR-MS-ESI(+) calc. C18H19N2O2S+ [M+H]+ 327.1162, found 327.1168.Synthesis of compound 5d A solution of ethyl 2-phenylacrylate (17.6 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 15 min. All the25 volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution withcontinuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5d (34.6 mg, 0.086 mmol, 86%).Characterization data of compound 5d:30 1H NMR (500 MHz, 298 K, C6D6): δ = [7.84 (2H), 7.25 (2H), 7.17 (2H), 7.03 (1H), 6.93 (2H), 6.90 (3H), 6.75(1H), 6.68 (2H)](each m, Ph), 4.03 (m, 2H, CH2Et), [3.97, 2.52](each d, each 2JHH = 13.0 Hz, each 1H, CH2),0.90 (t, 3JHH = 7.1 Hz, 3H, CH3Et). 45 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 172.6 (C=O), [145.1, 134.0, 133.3, 130.73, 130.67, 129.81,129.78, 128.7, 128.6, 128.3, 127.2, 127.0](Ph), 91.4 (C-N), 90.4 (S=C), 61.4 (CH2Et), 35.6 (CH2), 14.1 (CH3Et). IR (ATR) [cm-1]: ṽ = 3056, 2982, 2902, 2853, 2267, 2210, 2172, 2108, 1970, 1717, 1599, 1580, 1475, 1444,5 1389, 1337, 1243, 1146, 1121, 1072, 1022, 998, 896, 859, 812, 745, 689, 648, 614, 582, 518, 504, 483, 452. HR-MS-ESI(+) calc. C24H23N2O2S+ [M+H]+ 403.1475, found 403.1483.Synthesis of compound 5e 10 A solution of diethyl 2-(propan-2-ylidene) malonate (20.0 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperaturefor 15 min. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into thesolution with continuous stirring, during this time a light-yellow solid formed, which was collected by filtration15 and washed with cold n-pentane (1×1 mL) to give compound 5e (39.6 mg, 0.093 mmol, 93%).Characterization data of compound 5e: 1H NMR (500 MHz, 298 K, C6D6): δ = 7.60 (m, 4H, o-Ph), 6.93 (m, 6H, m,p-Ph), 4.10 (q, 3JHH = 7.1 Hz, 4H,CH2Et), 1.51 (s, 6H, Me), 0.99 (t, 3JHH = 7.1 Hz, 6H, CH3Et).20 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 167.6 (C=O), [137.6, 130.9, 129.9, 128.9](Ph), [98.8, 96.0](C-N, C=S), 60.7 (CH2Et), 48.2 (C(CH3)2), 24.5 (C(CH3)2), 14.1 (CH3Et). IR (ATR) [cm-1]: ṽ = 3056, 2980, 2903, 2871, 2138, 1719, 1579, 1475, 1443, 1384, 1363, 1242, 1190, 1158,1087, 1047, 1022, 997, 913, 848, 826, 746, 688, 627, 596, 563, 522, 506, 474. HR-MS-ESI(+) calc. C23H27N2O4S+ [M+H]+ 427.1687, found 427.1702.25 Synthesis of compound 5f A solution of diethyl 2-(4-methylbenzylidene) malonate (26.2 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperaturefor 15 min. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the30 solution with continuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5f (42.4 mg, 0.087 mmol, 87%). 46 Characterization data of compound 5f: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.51 (2H), 7.06 (2H), 6.96 (2H), 6.93 (1H), 6.74 (1H), 6.64 (2H)](eachm, Ph), 6.90 (m, 2H, o-C6H4), 6.59 (m, 2H, m-C6H4), 5.41 (s, 1H, CH), [4.25, 4.09, 3.67.3.61](each m, each5 1H, CH2Et), 1.97 (s, 3H, Me), [1.02, 0.66](each t, each 3JHH = 7.1 Hz, each 3H, CH3Et).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [168.9, 167.5](C=O), 136.6 (i-C6H4), 136.0 (p-C6H4), [135.2,134.5, 130.8, 130.4, 129.8, 129.4, 129.3, 128.5](Ph), 130.0 (o-C6H4), 128.6 (m-C6H4), [98.0, 94.6] (S=C, C- N), [61.9, 60.4](CH2Et), 51.3 (CH), 20.9 (Me), [14.1, 13.7](CH3Et). IR (ATR) [cm-1]: ṽ = 3055, 2981, 1755, 1720, 1579, 1512, 1475, 1443, 1390, 1365, 1331, 1298, 1244, 1208,10 1099, 1051, 1022, 998, 965, 894, 869, 845, 805, 745, 697, 614, 599, 573, 521, 504, 484, 452. HR-MS-ESI(+) calc. C28H29N2O4S+ [M+H]+ 489.1843, found 489.1866.Synthesis of compound 5g A solution of norbornene (47.0 mg, 0.5 mmol, 5 equiv.) in benzene (0.5 mL) was added dropwise to a15 solution of compound 3 (22.6 mg, 0.1 mmol) in benzene (0.5 mL) at stirred at room temperature for 12 h.All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution withcontinuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5g (29.1 mg, 0.091 mmol, 91%). Crystals of compound 5gsuitable for X-ray diffraction were obtained from a solution of the light-yellow solid in THF and pentane20 (ratio: 1: 3) at room temperature. Characterization data of compound 5g: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.35 (2H), 7.30 (2H), 6.88 (3H), 6.84 (3H)](each m, Ph), 4.66 (m,1H, CHb), 2.96 (m, 1H, CHd), 2.66 (m, 1H, CHa), 1.75 (m, 1H, CHc), [1.56, 1.00](each m, each 1H, CH2e),25 [1.37, 1.19](each m, each 1H, CH2g), [1.23, 1.03](each m, each 1H, CH2f). 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [137.9 (br), 137.2 (br), 130.3, 130.2, 129.6, 129.5, 128.7,128.5](Ph), 91.8 (C=S), 88.6 (CHb), 47.3 (CHa), 43.4 (CHc), 42.9 (CHd), 33.3 (CH2e), 28.0 (CH2f), 27.0 (CH2g). IR (ATR) [cm-1]: ṽ = 3058, 2869, 1676, 1575, 1474, 1442, 1378, 1235, 1127, 1115, 1098, 1068, 1022, 998,30 986, 952, 905, 745, 689, 616, 577, 566, 512, 475, 449, 422, 405. HR-MS-ESI(+) calc. C20H21N2S+ [M+H]+ 321.1420, found 321.1425. 47 Synthesis of compound 5h A solution of cyclopentene (136.2 mg, 2 mmol, 20 equiv.) in benzene (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in benzene (0.5 mL) at stirred at room temperature for 96 h.5 All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution withcontinuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5h (9.1 mg, 0.031 mmol, 31%).Characterization data of compound 5h:10 1H NMR (500 MHz, 298 K, C6D6): δ = 7.34 (m, 4H, o-Ph), 6.86 (m, 6H, m,p-Ph), 5.16 (m, 1H, CHa), 3.20(m, 1H, CHe), [2.46, 1.82](each m, each 1H, CH2b), [1.44, 1.32](each m, each 1H, CH2c), [1.40, 1.25](each m, each 1H, CH2d). 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [138.1, 138.0 (br), 130.3, 130.2, 129.6, 129.5, 128.8, 128.3](Ph),91.7 (S=C), 85.8 (CHa), 42.4 (CHe), 36.2 (CH2b), 34.0 (CH2d), 24.7 (CH2c).15 IR (ATR) [cm-1]: ṽ = 3361, 3055, 2920, 2850, 2214, 2141, 2046, 2001, 1984, 1656, 1633, 1580, 1472, 1442,1377, 1234, 1180, 1105, 1070, 998, 925, 876, 840, 793, 746, 690, 515, 489, 474, 452, 424. HR-MS-ESI(+) calc. C18H19N2S+ [M+H]+ 295.1263, found 295.1263.Synthesis of compound 5i 20 A solution of ethene-1,1-diyldibenzene (18.0 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 48 h. Allthe volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution withcontinuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5i (23.9 mg, 0.059 mmol, 59%).25 Characterization data of compound 5i: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.71 (4H), 7.17 (4H), 7.05 (2H), 6.98 (4H), 6.82 (2H), 6.77 (4H)](eachm, Ph), 3.01 (s, 2H, CH2). 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [148.0, 134.4, 130.5, 129.6, 128.37, 128.35, 127.8, 126.5](Ph),30 89.5 (C-N), 88.3 (C=S), 38.6 (CH2). IR (ATR) [cm-1]: ṽ = 3071, 2995, 2854, 1598, 1580, 1492, 1476, 1445, 1359, 1248, 1144, 1101, 1072, 1024,998, 747, 698, 581, 517. HR-MS-ESI(+) calc. C27H23N2S+ [M+H]+ 407.1577, found 407.1571. 48 Synthesis of compound 5j A solution of 4,4'-(ethene-1,1-diyl)bis(fluorobenzene) (21.6 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature5 for 48 h. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into thesolution with continuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5j (31.4 mg, 0.071 mmol, 71%).Characterization data of compound 5j:10 1H NMR (500 MHz, 298 K, C6D6): δ = [7.44 (o-), 6.81 (m-)](each m, each 4H, C6H4), 6.96 (m, 4H, o-Ph),6.79 (m, 2H, p-Ph), 6.77 (m, 4H, m-Ph), 2.82 (s, 2H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 162.0 (d, 1JFC = 244.5 Hz, p-C6H4), 143.5 (4JFC = 3.2 Hz, i-C6H4),134.1 (i-Ph), 130.7 (p-Ph), 129.7 (m-Ph), 129.3 (d, 3JFC = 7.7 Hz, o-C6H4), 128.3 (o-Ph), 115.0 (d, 2JFC =21.0 Hz, m-C6H4), 88.4 (C=S), 88.0 (C-N), 38.8 (CH2).1519F NMR (470 MHz, 298 K, C6D6): δ = -116.8. IR (ATR) [cm-1]: ṽ = 3056, 2978, 1599, 1580, 1505, 1476, 1444, 1407, 1358, 1225, 1158, 1105, 1068, 1015,998, 884, 836, 744, 688, 634, 617, 608, 569, 521, 479, 447, 422. HR-MS-ESI(+) calc. C27H21F2N2S+ [M+H]+ 443.1389, found 443.1397.Synthesis of compound 5k 20 A solution of 4,4'-(ethene-1,1-diyl)bis((trifluoromethyl)benzene) (31.6 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at roomtemperature for 15 min. All the volatiles were removed under reduced pressure, n-pentane (2 mL) wasadded into the solution with continuous stirring, during this time a light-yellow solid formed, which was25 collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5k (33.1 mg, 0.061mmol, 61%). Characterization data of compound 5k: 1H NMR (500 MHz, 298 K, C6D6): δ = 7.48 (m, 4H, o-C6H4), 7.35 (m, 4H, m-C6H4), 6.92 (m, 4H, o-Ph), 6.8230 (m, 2H, p-Ph), 6.78 (m, 4H, m-Ph), 2.79 (s, 2H, CH2). 49 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 150.9 (i-C6H4), 133.6 (i-Ph), 130.9 (p-Ph), 129.8 (m-Ph), 128.9(q, 2JFC = 32.2 Hz, p-C6H4), 128.3 (o-Ph), 128.0 (o-C6H4), 125.4 (q, 3JFC = 3.9 Hz, m-C6H4), 125.1 (q, 1JFC =272.0 Hz, CF3), 89.1 (C=S), 88.2 (C-N), 38.2 (CH2). 19F NMR (470 MHz, 298 K, C6D6): δ = -61.9. 5IR (ATR) [cm-1]: ṽ = 3355, 2920, 2850, 1659, 1632, 1615, 1471, 1444, 1410, 1325, 1164, 1116, 1068, 1017,842, 744, 688, 572, 516, 488, 449, 416. HR-MS-ESI(+) calc. C29H21F6N2S+ [M+H]+ 543.1325, found 543.1339.Synthesis of compound 5l 10 A solution of 2-(prop-1-en-2-yl)pyridine (11.9 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 24 h. Allthe volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution withcontinuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5l (26.2 mg, 0.076 mmol, 76%).15 Characterization data of compound 5l: 1H NMR (500 MHz, 298 K, C6D6): δ = [8.52, 8.11, 7.15, 6.63](each m, each 1H, CHC5H4N), [7.08(2H), 7.02(2H), 6.84 (1H), 6.82 (2H), 6.79 (1H), 6.74 (2H)](each m, Ph), [3.42, 2.57](each d, 2JHH = 13.1 Hz, each 1H,CH2), 1.95 (s, 3H, CH3).20 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [167.1, 148.9, 136.0, 122.1, 121.4](C5H4N), [134.9, 134.6, 130.4,130.2, 129.6, 129.5, 128.5, 128.3](Ph), 89.1 (C=S), 85.4(C), 37.0 (CH2), 28.0 (CH3). IR (ATR) [cm-1]: ṽ = 2965, 2878, 1473, 1386, 1111, 1068, 879, 835, 741, 690, 557.HR-MS-ESI(+) calc. C21H20N3S+ [M+H]+ 346.1372, found 346.1368.Synthesis of compound 5m 25 A solution of 1-(prop-1-en-2-yl)-4-(trifluoromethyl)benzene (18.6 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperaturefor 24 h. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into thesolution with continuous stirring, during this time a light-yellow solid formed, which was collected by filtration30 and washed with cold n-pentane (1×1 mL) to give compound 5m (39.1 mg, 0.079 mmol, 79%). 50 Characterization data of compound 5m: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.57, 7.39](each m, each 2H, C6H4), [7.09 (2H), 6.94 (2H), 6.89 (3H),6.78 (1H), 6.74 (2H)](each m, Ph), 2.39 (m, 2H, CH2), 1.62 (s, 3H, CH3). 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [153.4 (i-), 128.3 (m, p-), 126.9 (o-), 125.4 (q, 3JFC = 3.8 Hz, m)],5 [134.8, 134.1, 130.60, 130.58, 129.7, 128.4, 128.2](Ph), 127.4 (q, 1JFC = 272.0 Hz, CF3), 88.1 (C=S), 82.6(C), 39.3 (CH2), 29.6 (CH3). 19F NMR (470 MHz, 298 K, C6D6): δ = -61.9. IR (ATR) [cm-1]: ṽ = 2015, 1955, 1617, 1475, 1443, 1408, 1361, 1327, 1164, 1115, 1074, 1016, 845, 743,689, 561, 515.10 HR-MS-ESI(+) calc. C23H20F3N2S+ [M+H]+ 413.1294, found 413.1281.Synthesis of compound 5n A solution of 1-methyl-4-(3,3,3-trifluoroprop-1-en-2-yl)benzene (18.6 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room15 temperature for 15 min. All the volatiles were removed under reduced pressure, n-pentane (2 mL) wasadded into the solution with continuous stirring, during this time a light-yellow solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 5m (37.5 mg, 0.091mmol, 91%). 20 Characterization data of compound 5n: 1H NMR (500 MHz, 298 K, C6D6): δ = 7.91 (m, 2H, o-C6H4), [7.00 (2H), 6.84 (3H), 6.81 (2H), 6.76 (1H),6.68 (2H)](each m, Ph), 6.97 (m, 2H, m-C6H4), [3.15, 2.76](each d, 2JHH = 13.5 Hz, each 1H, CH2), 2.03 (s,3H, CH3). 13C{1H} NMR (125 MHz, 298 K, C6D6)[CF3 group was not listed]: δ = [137.7, 137.6, 129.3, 128.5](C6H4),25 [133.6, 132.8, 130.8, 129.82, 129.80, 128.3](Ph), 90.2 (C=S), 87.6 (q, 2JFC = 23.9 Hz, C-CF3), 33.0 (CH2),20.9 (CH3). 19F NMR (470 MHz, 298 K, C6D6): δ = -75.4. IR (ATR) [cm-1]: ṽ = 3360, 2920, 2850, 1659, 1633, 1511, 1472, 1444, 1341, 1278, 1232, 1142, 1063, 1022,998, 878, 813, 744, 728, 689, 619, 560, 517, 486, 424.30 HR-MS-ESI(+) calc. C23H20F3N2S+ [M+H]+ 413.1294, found 413.1307. 51 Synthesis of compound 6a Asolution of N-methylmaleimide (11.1 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 1 h. All the volatiles5 were removed under reduced pressure, n-pentane (2 mL) was added into the solution with continuousstirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 6a (14.9 mg, 0.099 mmol, 99%). Crystals of compound 6a suitable forX-ray diffraction were obtained from a solution of the colorless solid in dichloromethane and pentane (ratio: 1: 3) at room temperature. 10 Characterization data of compound 6a: 1H NMR (500 MHz, 298 K, CD2Cl2): δ = 11.20 (s, 1H, NH), 7.87 (s, 1H, CH), 3.09 (s, 3H, CH3).13C{1H} NMR (125 MHz, 298 K, CD2Cl2): δ = [162.4, 162.2](C=O), 153.6 (Ca), 125.9 (CH), 119.8 (Cb), 24.4(CH3).15 IR (ATR) [cm-1]: ṽ = 3122, 3059, 1785, 1764, 1718, 1647, 1580, 1491, 1475, 1439, 1365, 1237, 1180, 1081,1024, 977, 930, 876, 795, 737, 689, 639, 601, 583, 518, 495, 466, 428, 414. HR-MS-APCI(+) calc. C6H6N3O2+ [M+H]+ 152.0455, found 152.0438.Synthesis of compound 6b20 A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 1 h. All the volatileswere removed under reduced pressure, n-pentane (2 mL) was added into the solution with continuous25 stirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 6b (17.5 mg, 0.095 mmol, 95%).Characterization data of compound 6b: 1H NMR (500 MHz, 298 K, DMSO-d6): δ = 13.83 (br, 1H, NH), 8.40 (CH), [3.82, 3.74](each s, each 3H,30 each OMe). 13C{1H} NMR (125 MHz, 298 K, DMSO-d6)[selected resonances]: δ = [162.8 (br), 162.1](C=O), 133.5 (CH),[52.2, 51.5](OMe). 52 IR (ATR) [cm-1]: ṽ = 3164, 3127, 2958, 2922, 2129, 2039, 1746, 1718, 1700, 1509, 1459, 1431, 1370, 1348,1322, 1287, 1216, 1169, 1102, 1075, 974, 947, 903, 860, 824, 803, 795,764, 655, 625, 582, 504, 483, 470, 460, 448, 435, 424, 414. HR-MS-APCI(+) calc. C7H8N2NaO4+ [M+Na]+ 207.0377, found 207.0377.5 Synthesis of compound 6c Reaction of compound 3 and tert-butyl acrylate at room temperature Asolution of tert-butyl acrylate (12.8 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 1 h. All the volatiles10 were removed under reduced pressure, n-pentane (2 mL) was added into the solution with continuousstirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 6c (15.8 mg, 0.094 mmol, 94%).Characterization data of compound 6c:15 1H NMR (500 MHz, 298 K, CDCl3): δ = 11.53 (br, 1H, NH), 7.78 (d, 3JHH = 2.3 Hz, 1H, CHb), 6.78 (d, 3JHH =2.2 Hz, 1H, CHa), 1.61 (s, 9H, tBu).13C{1H} NMR (125 MHz, 298 K, CDCl3): δ = 160.0 (C=O), 140.1 (br, C=N), 134.7 (br, CHb), 108.4 (br, CHa),[82.8, 28.3](tBu). IR (ATR) [cm-1]: ṽ = 3254, 3130, 2978, 2936, 1698, 1519, 1477, 1453, 1393, 1367, 1303, 1252, 1223, 1145,20 1092, 1069, 1053, 982, 931, 838, 768, 626, 511, 467, 414. HR-MS-ESI(+) calc. C8H12N2NaO2+ [M+Na]+ 191.0791, found 191.0788.Synthesis of compound 6d Reaction of compound 3 and acrylonitrile at room temperature 25 A solution of acrylonitrile (5.3 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 1 h. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution with continuous stirring,during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane30 (1×1 mL) to give compound 6d (8.5 mg, 0.091 mmol, 91%). 53 Characterization data of compound 6d: 1H NMR (500 MHz, 298 K, CDCl3): δ = 8.19 (br, 1H, NH), 7.74 (d, 3JHH = 2.5 Hz, 1H, CHb), 6.80 (d, 3JHH =2.5 Hz, 1H, CHa). 13C{1H} NMR (125 MHz, 298 K, CDCl3): δ = 130.1 (CHb), 125.6 (C=N), 113.9 (CN), 111.3 (CHa).5 IR (ATR) [cm-1]: ṽ = 3274, 3147, 3132, 2247, 1509, 1456, 1419, 1374, 1348, 1310, 1272, 1179, 1089, 1058,980, 933, 884, 812, 780, 768, 686, 624, 584, 549, 494. HR-MS-ESI(+) calc. C4H4N3+ [M+H]+ 94.0400, found 94.0399.Synthesis of compound 6e10 Reaction of compound 3 and 1-fluoro-4-vinylbenzene at room temperature for 12 h A solution of 1-fluoro-4-vinylbenzene (12.2 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 12 h. All thevolatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution with15 continuous stirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 6e (12.4 mg, 0.077 mmol, 77%).Characterization data of compound 6e: 1H NMR (500 MHz, 298 K, C6D6): δ = 9.23 (br, 1H, NH), 7.62 (m, 2H, o-C6H4), 6.82 (m, 2H, m-C6H4), 6.8220 (m, 1H, CHb), 6.24 (d, 3JHH = 2.3 Hz, 1H, CHa).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 162.9 (d, 1JFC = 246.0 Hz, p-C6H4), 149.6 (br, C=N), 131.0 (br,CHb), 129.8 (br, i-C6H4), 127.7 (d, 3JFC = 7.8 Hz, o-C6H4), 115.7 (d, 2JFC = 21.8 Hz, m-C6H4), 102.2 (CHa).HR-MS-ESI(+) calc. C9H8FN2+ [M+H]+ 163.0667, found 163.0667.25 Synthesis of compound 6f A solution of styrene (10.4 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 12 h. All the volatiles were removed under reduced pressure, n-pentane (2 mL) was added into the solution with continuous stirring,30 during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane(1×1 mL) to give compound 6f (7.0 mg, 0.049 mmol, 49%).Characterization data of compound 6f: 54 1H NMR (500 MHz, 298 K, C6D6): δ = [7.81 (br, 2H, o-), 7.19 (m, 2H, m-), 7.09 (m, 1H, p-)](Ph), 6.91 (br,1H, CHb), 6.37 (d, 3JHH = 2.3 Hz, 1H, CHa) [NH was not listed].13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 150.0 (br, C=N), 133.3 (i-Ph), 131.7 (CHb), 128.9 (m-Ph), 127.9(p-Ph), 126.0 (o-Ph), 102.4 (CHa). 5IR (ATR) [cm-1]: ṽ = 3168, 3064, 2964, 2924, 2849, 1606, 1539, 1500, 1456, 1442, 1353, 1300, 1276, 1204,1113, 1095, 1071, 1046, 1028, 955, 932, 880, 755, 694, 613, 454. HR-MS-ESI(+) calc. C9H9N2+ [M+H]+ 145.0760, found 145.0759.Synthesis of compound 7a 10 A solution of N-methylmaleimide (33.3 mg, 0.3 mmol, 3.0 equiv.) in THF (0.5 mL) was added dropwise toa solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) at -40 oC in 5 min. The temperature wasslowly warmed up to room temperature and stirred at room temperature for another 30 min. All the volatiles were removed under reduced pressure, the remaining residue was purified by silica gel column chromatography (eluent: pentane / EtOAc = 3:1) to give compound 7a (17.5 mg, 0.067 mmol, 67%) as a colorless15 solid. Crystals of compound 7a suitable for X-ray diffraction were obtained from a solution of the colorlesssolid in dichloromethane and pentane (ratio: 1:3) at room temperature. Characterization data of compound 7a: 1H NMR (500 MHz, 298 K, CD2Cl2): δ = 6.00 (d, 3JHH = 8.2 Hz, CHa), [3.54, 3.49](each d, each 3JHH = 6.2Hz, CHc / CHd), 3.00 (d, 3JHH = 8.2 Hz, CHb), 2.99 (s, 3H, NbCH3), 2.94 (s, 3H, NaCH3).20 13C{1H} NMR (125 MHz, 298 K, CD2Cl2): δ = [171.6, 168.5](Na-C=O), [170.0, 169.8](Nb-C=O), 93.6 (CHa),82.5 (Cspir), 38.1 (CHb), [31.8, 29.5](CHc / CHd), 25.8 (NaCH3), 25.2 (NbCH3). IR (ATR) [cm-1]: ṽ = 3083, 3059, 2923, 2852, 2182, 2121, 1962, 1775, 1704, 1435, 1379, 1285, 1130, 1038,959, 892, 689. HR-MS-ESI(+) calc. C11H10N4NaO4+ [M+Na]+ 285.0595, found 285.0590.25 Synthesis of compounds 7b 55 A solution of di-tert-butyl 2-methylenemalonate (22.8 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in C6D6 (0.3 mL) and stirred at room temperature for 15min. A solution of N-methylmaleimide (11.1 mg, 0.1 mmol) in C6D6 (0.3 mL) was added to the reactionmixture. The reaction mixture was kept at 50 oC for 2 h. All the volatiles were removed under reduced5 pressure, and the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 4:1) to give compounds 7b-A and 7b-B (33.7 mg, 0.089 mmol, 89%, the ratio of 7b-Aand 7b-B is ca. 9:1) both as colorless solid. Crystals of compound 7b-A suitable for X-ray diffraction wereobtained from a solution of the colorless solid in ethyl acetate and pentane (ratio: 1:3) at room temperature. Characterization data of compounds 7b:10 1H NMR (500 MHz, 298 K, C6D6) for 7b-A: δ = 2.63 (s, 3H, NCH3), 2.12 (s, 2H, CH), 1.84 (s, 2H, CH2), 1.34(s, 18H, tBu).1H NMR (500 MHz, 298 K, C6D6) for 7b-B: δ = 2.75 (m, 2H, CH), 2.26 (s, 3H, NCH3), 2.24 (s, 2H, CH2),1.33 (s, 18H, tBu).13C{1H} NMR (125 MHz, 298 K, C6D6) for 7b-A: δ = 170.0 (N-C=O), 164.8 (O-C=O), 102.0 (Ca), [83.8,15 27.2](tBu), 82.2 (Cb), 34.0 (CH), 31.8 (CH2), 24.3 (NCH3). 13C{1H} NMR (125 MHz, 298 K, C6D6) for 7b-B: δ = 170.1 (N-C=O), 164.6 (O-C=O), 102.1 (Ca), [83.9,27.6](tBu), 81.5 (Cb), 30.2 (CH), 27.1 (CH2), 23.7 (NCH3). IR (ATR) [cm-1]: ṽ = 3074, 2982, 1772, 1726, 1704, 1544, 1435, 1371, 1308, 1291, 1263, 1216, 1151, 1126,1100, 1082, 1039, 999, 954, 922, 888, 848, 836, 811, 795, 743, 722, 699, 682, 607, 546, 515, 490, 467,20 412. HR-MS-ESI(+) calc. C18H25N3NaO6+ [M+Na]+ 402.1636, found 402.1625.Synthesis of compounds 7c A solution of methyl methacrylate (10.0 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution25 of compound 3 (22.6 mg, 0.1 mmol) in C6D6 (0.3 mL) and stirred at room temperature for 15 min. A solutionof N-methylmaleimide (11.1 mg, 0.1 mmol) in C6D6 (0.3 mL) was added in the reaction mixture. The reactionmixture was kept at 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remainingresidue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 4:1) to give compounds 7c-A and 7c-B (23.8 mg, 0.095 mmol, 95%, the ratio of 7c-A and 7c-B is ca. 5:4) both as colorless solid.30 Crystals of compound 7c-A suitable for X-ray diffraction were obtained from a solution of the colorless solidin ethyl acetate and pentane (ratio: 1: 3) at room temperature. Characterization data of compound 7c: 1H NMR (500 MHz, 298 K, C6D6) for 7c-A: δ = 3.20 (s, 3H, OCH3), 2.69 (s, 3H, NCH3), [2.22, 2.14](each d,each 3JHH = 5.4 Hz, each 1H, each CH), [1.60, 0.70](each d, each 2JHH = 13.6 Hz, each 1H, CH2), 1.29 (s,35 3H, CH3). 56 1H NMR (500 MHz, 298 K, C6D6) for 7c-B: δ = 3.20 (s, 3H, OCH3), [2.80, 2.75](each d, each 3JHH = 6.0 Hz,each 1H, each CH), 2.41 (s, 3H, NCH3), [1.78, 1.00](each d, each 2JHH = 13.4 Hz, each 1H, CH2), 1.30 (s,3H, CH3). 13C{1H} NMR (125 MHz, 298 K, C6D6) for 7c-A: δ = [170.4, 170.2](N-C=O), 169.7 (O-C=O), 94.1 (Ca), 82.25 (Cb), 52.5 (OCH3), 34.8 (CH2), [34.04, 33.97](CH), 24.3 (NCH3), 21.6 (CH3). 13C{1H} NMR (125 MHz, 298 K, C6D6) for 7c-B: δ = [170.5, 170.3](N-C=O), 169.4 (O-C=O), 93.9 (Ca), 81.7(Cb), 52.5 (OCH3), [30.23, 30.18](CH), 30.1 (CH2), 23.8 (NCH3), 21.6 (CH3). IR (ATR) [cm-1]: ṽ = 3076, 2924, 2852, 1778, 1737, 1702, 1541, 1435, 1382, 1280, 1205, 1175, 1126, 1013,988, 956, 895, 838, 799, 698, 634, 606.10 HR-MS-APCI(+) calc. C11H13N3NaO4+ [M+Na]+ 274.0799, found 274.0799.Synthesis of compound 7d Synthesis of compound 7d from the reaction of compound 3, di-tert-butyl 2-methylenemalonate anddimethyl fumarate 15 A solution of di-tert-butyl 2-methylenemalonate (22.8 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in C6D6 (0.3 mL) and stirred at room temperature for 15min. A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added in the reaction mixture. The reaction mixture was kept at 50 oC for 2 h. All the volatiles were removed under reduced20 pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc =5:1) to give compounds 7d (36.7 mg, 0.089 mmol, 89%) as a colorless solid. Crystals of compound 7dsuitable for X-ray diffraction were obtained from a solution of the colorless solid in ethyl acetate and pentane (ratio: 1: 5) at room temperature. 25 Characterization data of compound 7d: 1H NMR (500 MHz, 298 K, C6D6): δ = [3.73, 2.81](each d, each 3JHH = 6.8 Hz, each CH), [3.23, 3.20](eachs, each 3H, each OCH3), [2.77, 2.57](each d, each 2JHH = 14.6 Hz, each 1H, CH2), [1.33, 1.28](each s, each9H, each tBu).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [168.6, 168.0](C=OCOOMe), [165.2, 165.0](C=OCOOtBu), 101.5 (Ca),30 [83.3, 83.2, 27.64, 27.55](tBu), 79.0 (Cb), [52.0, 51.9](OCH3), [33.9, 31.4](CH), 29.9 (CH2). IR (ATR) [cm-1]: ṽ = 2978, 1730, 1533, 1437, 1395, 1370, 1340, 1304, 1275, 1259, 1212, 1171, 1142, 1125,1078, 1021, 950, 932, 892, 841, 782, 738, 714, 685, 646, 580, 467. HR-MS-ESI(+) calc. C19H28N2NaO8+ [M+Na]+ 435.1738, found 435.1735. 57 Synthesis of compound 7d from the reaction of compound 3, di-tert-butyl 2-methylenemalonate anddimethyl maleate A solution of di-tert-butyl 2-methylenemalonate (22.8 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise 5to a solution of compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) and stirred at room temperature for 15min. A solution of dimethyl maleate (14.4 mg, 0.1 mmol) in THF (0.5 mL) was added in the reaction mixture. The reaction mixture was kept at 50 oC for 2 h. All the volatiles were removed under reduced pressure, theremaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) togive compounds 7d (20.2 mg, 0.049 mmol, 49%) as a colorless solid.10 Synthesis of compounds 7e Asolution of methyl methacrylate (10.0 mg, 0.1 mmol) was added dropwise to a solution of compound 3(22.6 mg, 0.1 mmol) in C6D6 (0.3 mL) and stirred at room temperature for 15 min. A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added in the reaction mixture. The reaction mixture15 was kept at 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residuewas purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compounds 7e (25.8mg, 0.091 mmol, 91%) as a colorless solid. Characterization data of compound 7e (two diastereomers with ca.10: 9 ratio):20 1H NMR (500 MHz, 298 K, C6D6): δ = [3.83, 3.71, 2.77, 2.72](each d, each 3JHH = 6.7 Hz, each 1H, CH),[3.29, 3.25, 3.210, 3.207](each s, each 3H, OCH3a), [3.22, 3.13](each s, each 3H, OCH3b), [2.38, 2.26, 1.50, 1.39](each d, each 2JHH = 14.1 Hz, each 1H, CH2), [1.40, 1.36](each s, each 3H, CH3).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [170.0, 169.9](C=Ob), 168.9, 168.7, 166.2, 166.1](C=Oa), [93.4,93.3](Ca), [79.03, 78.98](Cb), [52.3, 52.2](OCH3a), [52.1, 52.0, 51.79, 51.77](OCH3b), [34.2, 33.2](CH2),25 [33.9, 31.2, 30.9](CH), 21.5 (CH3). IR (ATR) [cm-1]: ṽ = 2956, 1731, 1539, 1438, 1378, 1335, 1291, 1254, 1212, 1171, 1146, 1119, 1063, 1022,992, 945, 893, 785. HR-MS-ESI(+) calc. C12H16N2NaO6+ [M+Na]+ 307.0901, found 307.0899. 58 Synthesis of compound 7f A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5k (54.2 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was kept at5 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purifiedby silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7f (46.0 mg, 0.092 mmol,92%) as a colorless solid. Characterization data of compound 7f:10 1H NMR (500 MHz, 298 K, C6D6): δ = [7.29, 7.21](each m, each 2H, m-C6H4), [7.06, 6.96](each m, each2H, o-C6H4), [3.62, 2.75](each d, each 3JHH = 6.7 Hz, each 1H, each CH), [3.62, 3.01](each s, each 3H,each OMe), [2.31, 2.20](each d, each 2JHH = 14.2 Hz, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [168.8, 165.9](C=O), [146.1, 145.6](i-C6H4), [130.1, 130.0](eachq, each 2JFC = 34.5 Hz, p-C6H4), [127.4, 127.0](o-C6H4), 125.9 (m, m-C6H4), [124.6, 124.5](each q, each151JFC = 272.2 Hz, CF3), 97.2 (Ca), 78.0 (Cb), [52.2, 51.8](OMe), 35.9 (CH2), [33.3, 30.7](CH). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.4, -62.5. IR (ATR) [cm-1]: ṽ = 2957, 2170, 2123, 1732, 1617, 1439, 1412, 1325, 1212, 1167, 1119, 1071, 1017, 906,841, 677, 610, 517. HR-MS-ESI(+) calc. C23H18F6N2NaO4+ [M+Na]+ 523.1063, found 523.1063.20 Synthesis of compound 7g A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5i (40.6 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was kept at50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purified25 by silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7g (33.1 mg, 0.091 mmol,91%) as a colorless solid. Characterization data of compound 7g: 59 1H NMR (500 MHz, 298 K, C6D6): δ = [7.30 (2H), 7.26 (2H), 7.07 (2H), 7.01 (3H), 6.95 (1H)](each m, Ph),[3.70, 2.81](each d, each 3JHH = 6.6 Hz, each 1H, CH), [3.26, 3.12](each s, each 3H, OMe), [2.55,2.44](each d, each 2JHH = 14.1 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [169.0, 166.3](C=O), [143.3, 143.1, 128.81, 128.78, 127.7, 127.5,5 127.2, 127.0](Ph), 98.6 (Ca), 78.2 (Cb), [52.0, 51.7](OMe), 36.6 (CH2), [33.5, 30.9](CH). IR (ATR) [cm-1]: ṽ = 2955, 2926, 2854, 2158, 2025, 1733, 1602, 1494, 1438, 1334, 1261, 1209, 1066, 1026,905, 803, 750, 700, 509, 436, 414. HR-MS-ESI(+) calc. C21H21N2O4+ [M+H]+ 365.1496, found 365.1496.Synthesis of compound 7h 10 A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5j (44.2 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was kept at50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purifiedby silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7f (36.8 mg, 0.092 mmol,15 92%) as a colorless solid. Characterization data of compound 7h: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.00, 6.94](each m, each 2H, o-C6H4), [6.73, 6.67](each m, each 2H,m-C6H4), [3.67, 2.77](each d, each 3JHH = 6.6 Hz, CH), [3.26, 3.12](each s, each 3H, OMe), [2.35,20 2.27](each d, each 2JHH = 14.2 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [169.0, 166.1](C=O), [162.5, 162.3](each d, 1JFC = 246.9 Hz, p-C6H4), [138.9, 138.5](each d, each 4JFC = 3.2 Hz, i-C6H4), [128.9, 128.6](each d, each 3JFC = 8.2 Hz, o-C6H4), [115.7, 115.6](each d, each 2JFC = 21.3 Hz, m-C6H4), 97.2 (Ca), 78.1 (Cb), [52.1, 51.8](OMe), 36.6(CH2), [33.4, 30.8](CH). 2519F NMR (470 MHz, 298 K, C6D6): δ = -114.4, -114.5. IR (ATR) [cm-1]: ṽ = 2955, 2853, 1731, 1602, 1508, 1438, 1335, 1272, 1226, 1163, 1106, 1066, 1006, 905,837, 609, 542. HR-MS-ESI(+) calc. C21H19F2N2O4+ [M+H]+ 401.1307, found 401.1314. 60 Synthesis of compound 7i A solution of 4,4'-(ethene-1,1-diyl)bis(tert-butylbenzene) (29.2 mg, 0.1 mmol) was added dropwise to a solution of compound 3 (22.6 mg, 0.1 mmol) in C6D6 (0.3 mL) and stirred at room temperature for 96 h. A5 solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added in the reaction mixture. The reaction mixture was kept 50 oC for 2 h. All the volatiles were removed under reduced pressure, theremaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1)to give compounds 7i (17.6 mg, 0.037 mmol, 37%) as a colorless solid.10 Characterization data of compound 7i: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.36, 7.31](each m, each 2H, o-C6H4), [7.20, 7.15](each m, each 2H,m-C6H4), [3.76, 2.87](each d, each 3JHH = 6.6 Hz, each 1H, CH), [3.29, 3.14](each s, each 3H, OMe), [2.66,2.55](each d, each 2JHH = 14.1 Hz, each 1H, CH2), [1.18, 1.15](each s, each 9H, tBu).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [169.1, 166.4](C=O), [150.3, 150.2, 140.7, 140.5, 127.1, 126.8,15 125.8, 125.7](C6H4), 98.6 (Ca), 78.4 (Cb), [52.0, 51.7](OMe), 36.9 (CH2), [34.4, 34.3, 31.31, 31.28](tBu), [33.7, 31.1](CH). IR (ATR) [cm-1]: ṽ = 2959, 2905, 2867, 1731, 1509, 1437, 1396, 1364, 1334, 1305, 1268, 1208, 1144, 1111,1066, 1018, 1005, 905, 832, 803, 726, 705, 652, 579, 569. HR-MS-ESI(+) calc. C29H37N2O4+ [M+H]+ 477.2748, found 477.2739.20 Synthesis of compound 7j A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5l (34.5 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was kept at25 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purifiedby silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7j (26.0 mg, 0.086 mmol,86%) as a colorless solid. 61 Characterization data of compound 7j: 1H NMR (500 MHz, 298 K, C6D6) for major product: δ = [(8.38, 7.38, 7.03, 6.57](each m, C5H4N), [3.80,2.83](each d, each 3JHH = 6.4 Hz, each 1H, CH), [3.26, 3.23](each s, each 3H, OMe), [2.70, 2.01](each d,5 each 2JHH = 14.0 Hz, each 1H, CH2), 1.53 (s, 3H, Me).1H NMR (500 MHz, 298 K, C6D6) for minor product: δ = [(8.29, 7.38, 7.03, 6.57](each m, C5H4N), [3.79,2.87](each d, each 3JHH = 6.4 Hz, each 1H, CH), [3.31, 3.20](each s, each 3H, OMe), [2.74, 1.91](each d,each 2JHH = 14.0 Hz, each 1H, CH2), 1.56 (s, 3H, Me).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [168.93, 168.87, 166.57, 166.56](C=O), [161.17, 161.15, 149.5,10 149.4, 136.4, 136.3, 122.41, 122.38, 120.82, 120.76](C5H4N), [94.7, 94.6](Ca), [78.2, 78.0](Cb), [52.0, 51.9, 51.8, 51.6](OMe), [35.4, 35.3](CH2), [34.2, 33.4, 31.5, 30.8](CH), [25.5, 25.4](Me). IR (ATR) [cm-1]: ṽ = 2954, 1731, 1589, 1572, 1539, 1437, 1334, 1211, 1144, 1106, 1021, 993, 929, 894,787, 751, 622. HR-MS-ESI(+) calc. C15H18N3O4+ [M+H]+ 304.1292, found 304.1284.15 Synthesis of compound 7k A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5m (41.2 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was keptat 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purified20 by silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7k (32.9 mg, 0.089 mmol,89%) as a colorless solid. Characterization data of compound 7k: 1H NMR (500 MHz, 298 K, C6D6) for major product: δ = 7.30 (m, 2H, m-C6H4), 7.07 (m, 2H, o-C6H4), [3.68,25 2.71](each d, each 3JHH = 6.6 Hz, each 1H, CH), [3.30, 3.26](each s, each 3H, OMe), [1.87, 1.74](each d,each 2JHH = 17.9 Hz, each 1H, CH2), 1.14 (s, 3H, Me).1H NMR (500 MHz, 298 K, C6D6) for minor product: δ = 7.27 (m, 2H, m-C6H4), 7.06 (m, 2H, o-C6H4), [3.82,2.75](each d, each 3JHH = 6.6 Hz, each 1H, CH), [3.31, 3.15](each s, each 3H, OMe), 1.77 (m, 2H, CH2),1.24 (s, 3H, Me).30 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [169.0, 168.9, 166.3, 166.1](C=O), [148.0, 147.7](i-C6H4), [129.6,129.5](each q, each 2JFC = 32.5 Hz, p-C6H4), [126.2, 126.1](o-C6H4), 125.7 (m, m-C6H4), [124.83,124.81](each q, each 1JFC = 272.2 Hz, CF3), [91.7, 91.6](Ca), [77.4, 77.2](Cb), [52.14, 52.08, 51.9,51.8](OMe), [37.2, 36.1](CH2), [34.3, 32.9, 31.0, 30.1](CH), [26.5, 26.4](Me). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.26 (major isomer), -62.31 (minor isomer). 62 IR (ATR) [cm-1]: ṽ = 2957, 1733, 1619, 1439, 1410, 1328, 1213, 1168, 1122, 1083, 1066, 1016, 928, 845.HR-MS-ESI(+) calc. C17H18F3N2O4+ [M+H]+ 371.1213, found 371.1208.Synthesis of compound 7l 5 A solution of dimethyl fumarate (14.4 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5n (41.2 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was keptat 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purifiedby silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7k (29.2 mg, 0.079 mmol,10 79%) as a colorless solid. Characterization data of compound 7l: 1H NMR (500 MHz, 298 K, C6D6) for major product: δ = 7.41 (m, 2H, o-C6H4), 6.83 (m, 2H, m-C6H4), [3.72,2.78](each d, each 3JHH = 6.8 Hz, each 1H, CH), [3.27, 3.07](each s, each 3H, OMe), [2.50, 2.23](each d,15 each 2JHH = 14.6 Hz, each 1H, CH2), 1.95 (s, 3H, Me).1H NMR (500 MHz, 298 K, C6D6) for minor product: δ = 7.39 (m, 2H, o-C6H4), 6.85 (m, 2H, m-C6H4), [3.73,2.71](each d, each 3JHH = 6.8 Hz, each 1H, CH), [3.21, 3.20](each s, each 3H, OMe), [2.78, 2.08](each d,each 2JHH = 14.6 Hz, each 1H, CH2), 1.99 (s, 3H, Me).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [168.9, 168.6, 165.85, 165.79](C=O), [139.2, 132.2, 132.1,20 129.71, 129.69, 127.8](C6H4), [125.16, 125.22](each q, each 1JFC = 283.4 Hz, CF3), 96.6 (m, Ca), [79.5,79.3](Cb), [52.3, 52.12, 52.11, 51.8](OMe), [34.6, 34.0, 31.6, 31.2](CH), [31.1, 30.3](CH2), [20.94, 20.90](Me). 19F NMR (470 MHz, 298 K, C6D6): δ = -74.9 (major isomer), -75.1 (minor isomer). IR (ATR) [cm-1]: ṽ = 2957, 1730, 1514, 1438, 1336, 1297, 1265, 1213, 1159, 1084, 1009, 907, 813, 728,25 511. HR-MS-ESI(+) calc. C17H17F3N2NaO4+ [M+Na]+ 393.1033, found 393.1028.Synthesis of compound 7m 63 A solution of dimethyl fumarate (7.2 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5h (15.7 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was keptat 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purifiedby silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7m (10.4 mg, 0.042 mmol,5 83%) as a colorless solid. Characterization data of compound 7m: 1H NMR (500 MHz, 298 K, C6D6) for major product: δ = 4.50 (m, 1H, CHa), [4.04, 2.90](each d, each 3JHH =6.5 Hz, CH), [3.27, 3.25](each s, each 3H, OMe), [2.08, 1.51](each m, each 1H, CH2b), 1.99 (m, CHe), [1.27,10 0.80](each m, each 1H, CH2d), [1.00, 0.88](each m, each 1H, CH2c). 13C{1H} NMR (125 MHz, 298 K, C6D6) for major product: δ = [169.6, 166.4](C=O), 93.9 (CHa), 83.4 (Cf),[51.9, 51.8](OMe), 39.9 (CHe), [35.1, 29.96](CH), 31.1 (CH2d), 30.03 (CH2b), 24.3 (CH2c). IR (ATR) [cm-1]: ṽ = 3063, 2965, 2870, 1735, 1611, 1552, 1524, 1463, 1438, 1384, 1328, 1261, 1233, 1218,1190, 1164, 1061, 944, 902, 854, 808, 774, 756, 692, 661, 613, 585, 542, 513, 467.15 HR-MS-APCI(+) calc. C12H17N2O4+ [M+H]+ 253.1183, found 253.1190.Synthesis of compounds 7n 5k 7n A solution of acrylonitrile (5.3 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5k (54.2 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reaction mixture was kept at20 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remaining residue was purifiedby silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7n-A and 7n-B (38.4 mg,0.094 mmol, 94%, the ratio of 7n-A and 7n-B is ca. 10:9) both as colorless solid.Characterization data of compound 7n:25 1H NMR (500 MHz, 298 K, C6D6) for 7n-A: δ = [7.32, 7.28](each m, each 2H, m-C6H4), [7.16, 6.94](each m,each 2H, o-C6H4), [2.30, 1.64](each d, each 2JHH = 13.9 Hz, each 1H, CH2c), 1.61 (m, 1H, CH), [1.34,0.65](each m, each 1H, CH2d). 1H NMR (500 MHz, 298 K, C6D6) for 7n-B: δ = 7.29 (m, 4H, m-C6H4), 6.97 (m, 4H, o-C6H4), [1.61, 0.42](eachm, each 1H, CH2d), [1.35, 1.27](each d, each 2JHH = 13.4 Hz, each 1H, CH2c), 0.84 (m, 1H, CH).30 13C{1H} NMR (125 MHz, 298 K, C6D6) for 7n-A: δ = [146.7, 145.2](i-C6H4), [130.4, 130.2](each q, each 2JFC= 32.5 Hz, p-C6H4), [127.2, 127.0](o-C6H4), [126.1, 126.0](each q, each 3JFC = 3.7 Hz, m-C6H4), [124.53,124.50](each q, each 1JFC = 271.9 Hz, CF3), 117.2 (CN), 99.0 (Ca), 72.5 (Cb), 35.0 (CH2c), 18.4 (CH2d), 10.8(CH). 64 13C{1H} NMR (125 MHz, 298 K, C6D6) for 7n-B: δ = [146.3, 145.5](i-C6H4), [130.31, 130.30](each q, each2JFC = 32.5 Hz, p-C6H4), [127.3, 126.9](o-C6H4), [126.1, 125.9](each q, each 3JFC = 3.7 Hz, m-C6H4), 124.5(q, 1JFC = 272.3 Hz, CF3), 116.6 (CN), 99.0 (Ca), 71.3 (Cb), 36.9 (CH2c), 18.0 (CH2d), 10.4 (CH).19F NMR (470 MHz, 298 K, C6D6) for 7n-A: δ = -62.42, -62.44.5 19F NMR (470 MHz, 298 K, C6D6) for 7n-B: δ = -62.41, -62.44.IR (ATR) [cm-1]: 2247, 2171, 2120, 1617, 1412, 1326, 1168, 1118, 1071, 1016, 898, 840, 611.HR-MS-APCI(+) calc. C20H14F6N3+ [M+H]+ 410.1086, found 410.1104.Synthesis of compound 7o 10 A solution of di-tert-butyl 2-methylenemalonate (22.8 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution of compound 5k (54.2 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature. The reactionmixture was kept at 50 oC for 2 h. All the volatiles were removed under reduced pressure, the remainingresidue was purified by silica gel column chromatography (eluent: pentane / EtOAc = 5:1) to give compounds 7o(55.5 mg, 0.095 mmol, 95%) as a colorless solid. 15 Characterization data of compound 7o: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.34, 7.30](each m, each 2H, m-C6H4), [7.22, 7.13](each m, each2H, o-C6H4), [2.98, 2.08](each d, each 2JHH = 14.6 Hz, each 1H, CH2c), [2.66, 1.54](each d, each 2JHH = 5.8Hz, each 1H, CH2d), [1.32, 1.28](each s, each 9H, tBu).20 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [167.5, 164.3](C=O), [147.1, 146.1](i-C6H4), [130.00,129.97](each q, each 2JFC = 32.6 Hz, p-C6H4), [125.9, 125.7](each q, each 3JFC = 3.7 Hz, m-C6H4), 124.6(q, 1JFC = 273.6 Hz, CF3), 98.0 (Ca), 82.8 (Cb), [81.7, 78.5, 27.8, 27.7](tBu), 42.3 (Ce), 34.9 (CH2c), 23.3(CH2d). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.3, -62.5.25 IR (ATR) [cm-1]: ṽ = 2980, 1720, 1617, 1478, 1458, 1411, 1394, 1369, 1324, 1286, 1259, 1164, 1119, 1070,1018, 1007, 897, 843, 737, 603, 518, 468, 432. HR-MS-ESI(+) calc. C29H31F6N2O4+ [M+Na]+ 585.2183, found 585.2162. 65 Synthesis of compound 8a Asolution of compound 7a (26.2 mg, 0.1 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 165 oC for 48 h. All the volatiles were removed under reduced5 pressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8a (12.4 mg, 0.053 mmol, 53%). Crystals of compound 8a suitable for X-ray diffraction wereobtained from a solution of the colorless solid in C6D5Br at room temperature. 10 Characterization data of compound 8a: 1H NMR (500 MHz, 298 K, CD3CN): δ = [3.05, 2.88](each m, each 2H, CH), 2.80 (s, 6H, NMe).13C{1H} NMR (125 MHz, 298 K, CD3CN): δ = [173.3, 173.2](C=O), 44.4 (Cspir), [27.4, 24.0](CH), 24.8 (NMe).IR (ATR) [cm-1]: ṽ = 3092, 3061, 1761, 1702, 1437, 1381, 1298, 1271, 1197, 1125, 1034, 1019, 998, 946,865, 808, 719, 692, 652.15 HR-MS-ESI(+) calc. C11H11N2O4+ [M+H]+ 235.0714, found 235.0707.Synthesis of compounds 8c Thermolysis reaction of compound 7c-A 20 Asolution of compound 7c-A (25.1 mg, 0.1 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the residue with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to give25 compounds 8c (22.1 mg, 0.099 mmol, 99%). Crystals of compound 8c-A suitable for X-ray diffraction wereobtained from a solution of the colorless solid in C6D5Br at room temperature. Characterization data of compound 8c: 66 1H NMR (500 MHz, 298 K, C6D5Br) for compound 8c-A: δ = 3.42 (s, 3H, OCH3), 2.72 (s, 3H, NCH3), [2.47,2.39](each d, each 3JHH = 5.0 Hz, each CH), [1.55, 0.80](each d, each 2JHH = 4.8 Hz, CH2), 1.13 (s, 3H,CH3). 1H NMR (500 MHz, 298 K, C6D5Br) for compound 8c-B: δ = 3.45 (s, 3H, OCH3), 2.65 (s, 3H, NCH3), [2.43,5 2.32](each d, each 3JHH = 4.7 Hz, each CH), [1.74, 0.89](each d, each 2JHH = 5.5 Hz, CH2), 1.18 (s, 3H,CH3). 13C{1H} NMR (125 MHz, 298 K, C6D5Br) for compound 8c-A: δ = [172.9, 172.7](N-C=O), 171.7 (O-C=O),51.9 (OCH3), 41.1 (Cspir), [26.2, 24.7](CH), 25.6 (C), 24.3 (NCH3), 18.0 (CH2), 17.3 (CH3). 13C{1H} NMR (125 MHz, 298 K, C6D5Br) for compound 8c-B: δ = [172.7, 172.2](N-C=O), 171.6 (O-C=O),10 51.7 (OCH3), 40.8 (Cspir), [26.7, 25.6](CH), 24.0 (NCH3), 23.4 (C), 19.8 (CH2), 16.4 (CH3). IR (ATR) [cm-1]: ṽ = 2961, 1979, 1768, 1714, 1702, 1433, 1381, 1323, 1269, 1190, 1163, 1138, 1072, 1015,978, 947, 895, 828, 672. HR-MS-ESI(+) calc. C11H13NNaO4+ [M+Na]+ 246.0737, found 246.0739.15 Thermolysis reaction of compound 7c-B Asolution of compound 7c-B (25.1 mg, 0.1 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the residue with continuous stirring, during this time a colorless20 solid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompounds 8c (22.1 mg, 0.099 mmol, 99%).Synthesis of compound 8e Asolution of compounds 7e (14.2 mg, 0.05 mmol, two isomers, ca.1:1) in C6D5Br (0.5 mL) was transferred25 into a J-Young NMR tube. The reaction mixture was kept at 130 oC for 3 h. The 1H NMR shows a quantitativetransformation to 8e. All the volatiles were removed under reduced pressure to give compound 8e (12.2mg, 0.048 mmol, 95%) as a colorless oil. Characterization data of compound 8e: 67 1H NMR (500 MHz, 298 K, C6D5Br): δ = [3.48, 3.45, 3.44, 3.41](each s, each 3H, OMea), [3.42, 3.38](eachs, each 3H, OCH3b), [2.83, 2.80, 2.65, 2.61](each d, 3JHH = 3.9 Hz, each 1H, CH), [1.83, 1.69, 1.07,1.05](each d, 2JHH = 5.0 Hz, each 1H, CH2), [1.33, 1.23](CH3).13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [172.9, 172.5](C=Ob), [170.2, 170.1, 169.9, 169.7](C=Oa),5 [51.85, 51.80, 51.78](OCH3a), [51.6, 51.4](OCH3b), [37.3, 37.0](Cspir), [28.8, 28.1, 28.0, 26.8](CH), [25.2, 24.3](C), [20.9, 20.1](CH2), [17.6, 16.5](CH3). IR (ATR) [cm-1]: ṽ = 2955, 2920, 2850, 1729, 1632, 1437, 1323, 1266, 1197, 1171, 1150, 1108, 1064, 1016,899, 755. HR-MS-ESI(+) calc. C12H16NaO6+ [M+Na]+ 279.0840, found 279.0836.10 Synthesis of compound 8f Asolution of compound 7f (25.0 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorless15 solid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8f (23.4 mg, 0.05 mmol, 99%). Crystals of compound 8f suitable for X-ray diffraction wereobtained from a solution of the colorless solid in C6H6 and pentane (ratio 1:1) at room temperature. Characterization data of compound 8f:20 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.47 (s), 7.26 (m)](each 2H, m-C6H4), [7.47 (s), 6.79 (m)](each 2H,o-C6H4), [3.36, 3.09](each s, each 3H, OCH3), [2.91, 2.87](each d, each 3JHH = 3.6Hz, CH), [1.95, 1.87](eachd, each 2JHH = 6.1 Hz, CH2).13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [169.65, 169.55](C=O), [146.0, 144.3](i-C6H4), [130.7,126.3](o-C6H4), [129.4 (m), 128.0 (q, 2JFC = 32.4 Hz)](p-C6H4), [125.8, 124.8](each q, each 3JFC = 3.7 Hz,25 m-C6H4), [124.4, 124.3](each q, each 1JFC = 272.2 Hz, CF3), [51.8, 51.6](OCH3), 39.4 (Cspir), 33.9 (CAr2),[28.6, 28.0](CH), 23.0 (CH2). 19F NMR (470 MHz, 298 K, C6D5Br): δ = -61.48, -61.54. IR (ATR) [cm-1]: ṽ = 2952, 2933, 2125, 1729, 1618, 1438, 1411, 1323, 1198, 1166, 1120, 1070, 1013, 936,900, 851, 795, 681, 609.30 HR-MS-ESI(+) calc. C23H19F6O4+ [M+H]+ 473.1183, found 473.1197.Synthesis of compound 8g 68 Asolution of compound 7g (18.2 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorless5 solid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8g (16.0 mg, 0.048 mmol, 95%).Characterization data of compound 8g: 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.46 (2H), 7.23 (2H), 7.13 (1H), 7.03 (2H), 6.99 (1H), 6.8810 (2H)](each m, Ph), [3.29, 3.12](each s, each 3H, OMe), [2.99, 2.90](each d, each 3JHH = 3.7 Hz, each 1H,CH), [1.91, 1.85](each d, each 2JHH = 5.7 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [170.1, 169.9](C=O), [142.6, 141.3, 130.2, 128.7, 127.9, 127.2,126.1, 125.7](Ph), [51.6, 51.5](OMe), 39.3 (Cspir), 34.4 (CPh2), [29.1, 28.0](CH), 22.8 (CH2) IR (ATR) [cm-1]: ṽ = 2952, 1730, 1618, 1497, 1437, 1369, 1325, 1197, 1168, 1125, 1072, 1012, 937, 899,15 846, 806, 757, 703, 604. HR-MS-ESI(+) calc. C21H20O4Na+ [M+Na]+ 359.1254, found 359.1255.Synthesis of compound 8h 20 A solution of compound 7h (20.0 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8h (18.0 mg, 0.048 mmol, 97%).25 Characterization data of compound 8h: 69 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.32, 6.73](each m, each 2H, o-C6H4), [6.87, 6.73](each m, each2H, m-C6H4), [3.35, 3.14](each s, each 3H, OMe), [2.91, 2.86](each d, each 3JHH = 3.6 Hz, each 1H, CH),[1.83, 1.75](each d, each 2JHH = 5.9 Hz, each 1H, CH2)13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [169.91, 169.86](C=O), [161.9, 161.1](each d, each 1JFC =5 246.6 Hz, p-C6H4), [138.2, 136.9](each d, each 4JFC = 3.2 Hz, i-C6H4), [131.8, 127.6](each d, each 3JFC =8.0 Hz, o-C6H4), [115.6, 114.7](each d, each 2JFC = 21.2 Hz, m-C6H4), [51.7, 51.6](OMe), 39.3 (Cspir), 33.2(CAr2), [28.9, 28.1](CH), 22.8 (CH2). 19F NMR (470 MHz, 298 K, C6D5Br): δ = -113.5, -116.1. IR (ATR) [cm-1]: ṽ = 2953, 1729, 1605, 1511, 1437, 1324, 1267, 1224, 1197, 1169, 1074, 1014, 934, 900,10 841, 795, 777, 553. HR-MS-ESI(+) calc. C21H18F2O4Na+ [M+Na]+ 395.1065, found 395.1070.Synthesis of compound 8i 15 A solution of compound 7i (23.8mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8i (21.5 mg, 0.048 mmol, 96%).20 Characterization data of compound 8i: 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.48, 6.85](each m, each 2H, o-C6H4), [7.32, 7.01](each m, each2H, m-C6H4), [3.25, 3.13](each s, each 3H, OMe), [3.09, 2.88](each d, each 3JHH = 3.7 Hz, each 1H, CH),[1.95, 1.92](each d, each 2JHH = 5.7 Hz, each 1H, CH2), [1.21, 1.15](each s, each 9H, tBu).25 13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [170.2, 170.0](C=O), [149.6, 148.1](p-C6H4), [139.5, 138.7](i-C6H4), [129.9, 126.1](o-C6H4), [125.6, 124.6](m-C6H4), [51.5, 51.4](OMe), 39.4 (Cspir), [34.3, 34.0, 31.4, 31.3](tBu), 33.8 (CAr2), [29.2, 28.0](CH), 22.3 (CH2). IR (ATR) [cm-1]: ṽ = 2960, 2904, 2867, 1731, 1512, 1436, 1396, 1363, 1318, 1268, 1196, 1168, 1113, 1073,1019, 934, 898, 841, 791, 581.30 HR-MS-ESI(+) calc. C29H37O4+ [M+H]+ 449.2686, found 449.2685. 70 Synthesis of compound 8j Asolution of compounds 7j (15.2 mg, 0.05 mmol, two isomers, ca.5:4) in C6D5Br (0.5 mL) was transferredinto a J-Young NMR tube. The reaction mixture was kept at 130 oC for 3 h. The 1H NMR shows a quantitative5 transformation to 8j. All the volatiles were removed under reduced pressure to give compound 8j (13.2 mg,0.048 mmol, 96%) as a colorless oil. Characterization data of compound 8j: 1H NMR (500 MHz, 298 K, C6D5Br): δ = [8.40 (1H), 8.34 (1H), 7.26 (1H), 7.23 (1H), 7.13 (1H), 6.98 (1H),6.74 (2H)](each m, C5H4N), [3.51, 3.46, 3.44, 2.99](each s, each 3H, OMe), [2.93, 2.73, 2.72, 2.58](each10 d, each 3JHH = 3.7 Hz, each 1H, CH), [2.15, 2.02, 1.27, 1.22](each d, each 2JHH = 4.7 Hz, each 1H, CH2),[1.50, 1.43](each s, each 3H, Me). 13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [170.6, 170.58, 170.56, 170.0](C=O), [161.8, 161.2, 149.0,148.7, 135.7, 135.3, 120.6, 120.3, 120.0, 119.8](C5H4N), [51.7, 51.6, 51.1](OMe), [40.0, 39.0](Cspir), [29.4, 28.6, 28.1, 26.7](CH), [28.8, 25.8](C), [22.0, 20.5](CH2), [19.7, 19.5](Me).15 IR (ATR) [cm-1]: ṽ = 2954, 1729, 1589, 1473, 1435, 1323, 1267, 1198, 1168, 1017, 769, 748.HR-MS-ESI(+) calc. C15H18NO4+ [M+H]+ 276.1230, found 276.1223.Synthesis of compound 8k Asolution of compound 7k (18.5 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMR20 tube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8k (16.1 mg, 0.047 mmol, 94%).25 Characterization data of compound 8k: 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.36, 7.32](each m, each 2H, m-C6H4), [7.30, 6.97](each m, each2H, o-C6H4), [3.54, 3.51, 3.39, 2.93](each s, each 3H, OMe), [2.77 (m, 2H), 2.71 (d, 3JHH = 3.6 Hz, 1H), 2.65(d, 3JHH = 3.6 Hz, 1H)](CH), [1.51, 1.40, 1.23, 1.20](each d, each 2JHH = 5.9 Hz, each 1H, CH2), [1.39,1.28](each s, each 3H, Me). 71 13C{1H} NMR (125 MHz, 298 K, C6D5Br)[p-C6H4 and CF3 are not listed, see spectrum below]: δ = [170.6,170.15, 170.14, 169.2](C=O), [147.85, 146.6](i-C6H4), [127.6, 125.5](o-C6H4), [125.4, 123.7](each q, each 3JFC = 3.8 Hz, o-C6H4), [51.9, 51.8, 51.7, 51.1](OMe), [39.7, 37.5](Cspir), [28.7, 28.3, 27.6, 26.6](CH), [26.1,24.0](C), [22.7, 22.2](CH2), [21.0, 19.2](Me). 519F NMR (470 MHz, 298 K, C6D5Br): δ = -61.3, -61.4. IR (ATR) [cm-1]: ṽ = 2956, 1731, 1619, 1438, 1327, 1199, 1164, 1119, 1068, 1015, 844, 780, 699.HR-MS-ESI(+) calc. C17H17F3O4Na+ [M+Na]+ 365.0971, found 365.0973.Synthesis of compound 8l 10 Asolution of compound 7l (18.5 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 150 oC for 6 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to give15 compound 8l (15.6 mg, 0.046 mmol, 91%).Characterization data of compound 8l: 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.39, 7.18](each m, each 2H, o-C6H4), [6.94, 6.92](each d, each20 2H, m-C6H4), [3.55, 3.50, 3.25, 3.24](each s, each 3H, OMe), [3.15 (d, 3JHH = 4.2 Hz, 1H), 2.88 (m, 2H),2.61 (d, 3JHH = 4.2 Hz, 1H)](CH), [2.21, 2.07](each s, each 3H, Me), [1.91, 1.78, 1.69, 1.61](each d, each2JHH = 6.1 Hz, each 1H, CH2). 13C{1H} NMR (125 MHz, 298 K, C6D5Br): δ = [169.60, 169.59, 169.4, 169.0](C=O), [138.5, 138.0](p-C6H4),[130.6, 129.4](o-C6H4), [130.1, 129.04](i-C6H4), [129.6, 129.01](m-C6H4), [52.05, 52.01, 51.8, 51.7](OMe),25 [32.8, 32.7] (m, Cspir / C-CF3), [28.8, 27.3, 26.6, 26.1](CH), [21.2, 21.1](Me), [15.2, 15.1](each m, CH2). 19F NMR (470 MHz, 298 K, C6D5Br): δ = -67.5, -67.6. IR (ATR) [cm-1]: ṽ = 2956, 1733, 1516, 1438, 1325, 1252, 1200, 1172, 1097, 1017, 809, 572, 411.HR-MS-ESI(+) calc. C17H17F3O4Na+ [M+Na]+ 365.0971, found 365.0971. 72 Synthesis of compounds 8n Thermolysis reaction of compound 7n-A5 A solution of compound 7n-A (20.4 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-YoungNMR tube. The reaction mixture was kept at 150 oC for 6 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the residue with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompounds 8n (18.7 mg, 0.049 mmol, 98%).10 Thermolysis reaction of compound 7n-BA solution of compound 7n-B (20.4 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-YoungNMR tube. The reaction mixture was kept at 150 oC for 6 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the residue with continuous stirring, during this time a colorless15 solid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompounds 8n (18.7 mg, 0.049 mmol, 98%).Characterization data of compound 8n: 1H NMR (500 MHz, 298 K, C6D5Br) for major isomer: δ = [7.38, 7.36](each m, each 2H, m-C6H4), [6.87,20 6.86](each m, each 2H, o-C6H4), [1.86, 1.58](each d, each 2JHH = 5.7 Hz, each 1H, CH2a), 1.53 (m, 1H, CH),[1.36, 1.34](each m, each 1H, CH2b). 1H NMR (500 MHz, 298 K, C6D5Br) for minor isomer: δ = [7.41, 7.39](each m, each 2H, m-C6H4), [7.08,7.04](each m, each 2H, o-C6H4), [1.61, 1.49](each d, each 2JHH = 5.7 Hz, each 1H, CH2a), 1.58 (m, 1H, CH),[1.30, 1.07](each m, each 1H, CH2b).25 13C{1H} NMR (125 MHz, 298 K, C6D5Br) for major isomer [CF3 group were not listed]: δ = 145.3 (i-C6H4),[128.94, 128.91](each q, each 2JFC = 32.5 Hz, p-C6H4), [128.5, 128.1](o-C6H4), [125.7, 125.6](each q, each3JFC= 3.6 Hz, m-C6H4), 119.2 (CN), 34.2 (CAr2), 31.0 (Cspir), 22.8 (CH2a), 14.8 (CH2b), 5.1 (CH).13C{1H} NMR (125 MHz, 298 K, C6D5Br) for minor isomer [CF3 group and p-C6H4 were not listed]: δ = [145.2,144.0](i-C6H4), [129.1, 128.4](o-C6H4), [125.7, 125.3](each m, m-C6H4), 118.8 (CN), 33.8 (CAr2), 29.2 (Cspir),30 23.4 (CH2a), 14.4 (CH2b), 5.4 (CH). 19F NMR (470 MHz, 298 K, C6D5Br) for major isomer: δ = -61.495, -61.503. 19F NMR (470 MHz, 298 K, C6D5Br) for minor isomer: δ = -61.47, -61.50. IR (ATR) [cm-1]: ṽ = 1618, 1411, 1325, 1166, 1121, 1070, 1013, 841.HR-MS-ESI(+) calc. C20H14F6N+ [M+H]+ 382.1025, found 382.1029. 73 Synthesis of compound 8o Asolution of compound 7o (29.2 mg, 0.05 mmol) in C6D5Br (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 130 oC for 3 h. All the volatiles were removed under reduced5 pressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 8o (27.5 mg, 0.05 mmol, 99%).Characterization data of compound 8o:10 1H NMR (500 MHz, 298 K, C6D5Br): δ = [7.54, 7.33](each m, each 2H, m-C6H4), [7.54, 7.13](each m, each2H, o-C6H4), [1.92, 1.80](each d, each 2JHH = 5.5 Hz, each 1H, CH2a), [1.92, 1.64](each d, each 2JHH = 4.7Hz, each 1H, CH2b), [1.51, 1.06](each d, each 9H, tBu).13C{1H} NMR (125 MHz, 298 K, C6D5Br)[CF3 groups were not listed]: δ = [167.6, 166.6](C=O), [147.9,144.8](i-C6H4), [131.7, 126.5](o-C6H4), 127.5 (q, 2JFC = 32.1 Hz, p-C6H4), [125.7, 124.8](each q, each 3JFC15 = 3.7 Hz, m-C6H4), [81.7, 81.3, 28.0, 27.5](tBu), 38.4 (Cspir), 36.1 (C(COOtBu)2), 33.8 (CAr2), 28.3 (CH2a),20.7 (CH2b). 19F NMR (470 MHz, 298 K, C6D5Br): δ = -61.44, -61.46. IR (ATR) [cm-1]: ṽ = 2980, 1720, 1619, 1458, 1394, 1370, 1326, 1291, 1258, 1166, 1124, 1072, 1011, 841,805, 741, 610.20 HR-MS-ESI(+) calc. C23H19F6O4+ [M+H]+ 579.1940, found 579.1938.Synthesis of compound 9a A solution of paraformaldehyde (1.5 mg, 0.05 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 5i (20.3 mg, 0.05 mmol) in THF (0.5 mL) at room temperature. The reaction mixture was stirred25 at room temperature for 15 min. All the volatiles were removed under reduced pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compounds 9a(11.8 mg, 0.047 mmol, 94%) as a colorless solid. 74 Characterization data of compound 9a: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.30 (2H), 7.14 (2H), 7.06 (4H), 7.00 (2H)](each m, Ph), [3.23,2.47](each d, each 2JHH = 5.3 Hz, each 1H, OCH2), 2.09 (m, 2H, CH2).5 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [143.8, 142.8, 128.87, 128.85, 127.28, 127.75, 127.25,127.21](Ph), 98.6 (C(Ph)2), 93.8 (Cspir), 51.5 (OCH2), 34.8 (CH2). IR (ATR) [cm-1]: ṽ = 3059, 3027, 2924, 2852, 1788, 1726, 1598, 1547, 1493, 1475, 1447, 1384, 1273, 1186,1082, 1055, 1015, 926, 854, 820, 746, 699, 654, 595, 557, 521, 485, 443. HR-MS-ESI(+) calc. C16H15N2O+ [M+H]+ 251.1179, found 251.1166.10 A solution of paraformaldehyde (1.5 mg, 0.05 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 5k (27.1 mg, 0.05 mmol) in THF (0.5 mL) at room temperature. The reaction mixture was stirredat room temperature for 15 min. All the volatiles were removed under reduced pressure, the remaining15 residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compounds 9b(18.3 mg, 0.048 mmol, 95%) as a colorless solid. Characterization data of compound 9b: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.27, 7.23](each m, each 2H, m-C6H4), [7.01, 6.95](each m, each20 2H, o-C6H4), [3.24, 2.46](each d, each 2JHH = 5.0 Hz, each 1H, OCH2), 1.81 (s, 2H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [146.2, 145.7](i-C6H4), [130.3, 130.2](each q, 2JFC = 32.6 Hz, p-C6H4), [127.4, 127.3](o-C6H4), 126.0 (m, m-C6H4), [124.6, 124.5](each q, 1JFC = 272.2 Hz, CF3), 97.5(C(Ar)2), 93.8 (Cspir), 51.4 (OCH2), 33.9 (CH2). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.48, -62.47.25 IR (ATR) [cm-1]: ṽ = 2044, 1995, 1617, 1552, 1477, 1444, 1412, 1386, 1321, 1261, 1165, 1113, 1068, 1012,917, 839, 821, 758, 736, 692, 672, 614, 516, 464, 429. HR-MS-ESI(+) calc. C18H13F6N2O+ [M+H]+ 387.0927, found 387.0930. 75 Synthesis of compound 9c A solution of 1-methyl-pyrazole-4-carbaldehyde (5.5 mg, 0.05 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 5k (27.1 mg, 0.05 mmol) in THF (0.5 mL) at room temperature. The reaction5 mixture was stirred at 50 oC for 12 h. All the volatiles were removed under reduced pressure, n-pentane (1mL) was added into the solution with continuous stirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to give compound 9c (16.1 mg, 0.034mmol, 69%). 10 Characterization data of compound 9c: 1H NMR (500 MHz, 298 K, C6D6): δ = 7.35 (s, 1H, CHb), [7.28, 7.17](each m, each 2H, m-C6H4), [7.03,6.91](each m, each 2H, o-C6H4), 6.43 (s, 1H, CHa), 4.62 (s, 1H, CH), 3.12 (s, 3H, CH3), [2.23, 1.93](eachd, 2JHH = 14.5 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6)[CF3 groups were not listed]: δ = [146.8, 144.8](i-C6H4), 137.5 (CHb),15 [133.23, 133.20](each q, each 2JFC = 32.4 Hz, p-C6H4), 129.0 (CHa), [127.5, 127.4](o-C6H4), [126.0,125.9](each q, each 3JFC = 3.9 Hz, m-C6H4), 115.2 (i-C3N2), 100.7 (Cspir), 97.0 (C(Ar)2), 57.0 (CH), 38.4(CH3), 32.5 (CH2). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.4, -62.5. IR (ATR) [cm-1]: ṽ = 1617, 1411, 1323, 1166, 1117, 1070, 1015, 985, 915, 841, 756, 674, 615.20 HR-MS-ESI(+) calc. C22H17F6N4O+ [M+H]+ 467.1302, found 467.1305. A solution of thiophene-2-carbaldehyde (5.6 mg, 0.05 mmol) in THF (0.5 mL) was added dropwise to a solution of compound 5k (27.1 mg, 0.05 mmol) in THF (0.5 mL) at room temperature. The reaction mixture25 was stirred at room temperature for 12 h. All the volatiles were removed under reduced pressure, n-pentane(1 mL) was added into the residue with continuous stirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to give compound 9d (20.4 mg, 76 0.044 mmol, 87%). Crystals of compound 9d suitable for X-ray diffraction were obtained from a solution ofthe colorless solid in ethyl acetate and n-pentane (ratio 1:10) at room temperature.Characterization data of compound 9d: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.25, 7.17](each m, each 2H, m-C6H4), [6.96, 6.84](each m, each5 2H, o-C6H4), [6.76 (1H), 6.61 (2H)](each m, C4H3S), 4.80 (s, 1H, CH), [2.28, 2.00](each d, 2JHH = 14.7 Hz,each 1H, CH2). 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [146.2, 144.1](i-C6H4), [136.5, 127.1, 127.0, 126.0](C4S),[129.94, 129.88](each q, each 2JFC = 32.4 Hz, p-C6H4), [127.3, 126.9](o-C6H4), [125.7, 125.6](each q, each3JFC = 3.7 Hz, m-C6H4), [124.3, 124.2](each q, 1JFC = 272.4 Hz, CF3), 100.6 (Cspir), 96.6 (C(Ar)2), 59.4 (CH),10 32.1 (CH2). IR (ATR) [cm-1]: ṽ = 1617, 1411, 1325, 1167, 1119, 1070, 1012, 911, 840, 706, 604, 434.HR-MS-ESI(+) calc. C22H15F6N2OS+ [M+H]+ 469.0804, found 469.0805.Synthesis of compound 9e 15 A solution of [1,1’-biphenyl]-4-carbaldehyde (9.1 mg, 0.05 mmol) in THF (0.5 mL) was added dropwise to asolution of compound 5k (27.1 mg, 0.05 mmol) in THF (0.5 mL) at room temperature. The reaction mixturewas stirred at 40 oC for 12 h. All the volatiles were removed under reduced pressure, n-pentane (1 mL) wasadded into the residue with continuous stirring, during this time a colorlesss solid formed, which was20 collected by filtration and washed with cold n-pentane (1×0.5 mL) to give compound 9e (21.8 mg, 0.040mmol, 81%). Crystals of compound 9e suitable for X-ray diffraction were obtained from a solution of thecolorless solid in ethyl acetate and n-pentane (ratio 1:10) at room temperature.Characterization data of compound 9e: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.43 (4H), 7.21 (2H), 7.13 (1H), 6.98 (2H)](each m, Ph-C6H4), [7.29,25 7.14](each m, each 2H, m-C6H4), [6.99.6.78](each m, each 2H, o-C6H4), 4.72 (s, 1H, CH), [2.06, 1.86](eachd, each 2JHH = 14.6 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [147.0, 144.2](i-C6H4), [142.4, 140.4, 132.5, 129.2, 128.1,127.32, 127.30, 126.7](Ph-C6H4), [130.22, 130.18](each q, each 2JFC = 32.6 Hz, p-C6H4), [127.6, 127.4](o-C6H4), [126.0, 125.8](each q, each 3JFC = 3.7 Hz, m-C6H4), [124.61, 124.55](each q, each 1JFC = 272.4 Hz,30 CF3), 100.6 (Cspir), 96.7 (C(Ar)2), 62.4 (CH), 32.0 (CH2). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.4, -62.5. IR (ATR) [cm-1]: ṽ = 2046, 1616, 1488, 1410, 1322, 1165, 1117, 1069, 1012, 914, 840, 764, 697, 670, 604,519, 432. HR-MS-APCI(+) calc. C30H21F6N2O+ [M+H]+ 539.1553, found 539.1551. 77 Synthesis of compound 10a Asolution of compound 9a (12.5 mg, 0.05 mmol) in C6D6 (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 80 oC for 12 h. All the volatiles were removed under reduced5 pressure, n-pentane (1 mL) was added into the residue with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 10a (10.1 mg, 0.046 mmol, 91%).Characterization data of compound 10a:10 1H NMR (500 MHz, 298 K, C6D6): δ = [7.40 (2H), 7.16 (2H), 7.06 (3H), 7.00 (3H)](each m, Ph), [2.92,2.81](each d, 2JHH = 5.1 Hz, each 1H, OCH2), [1.71, 1.64](each d, 2JHH = 6.8 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [143.4, 141.9, 129.6, 128.62, 128.56, 128.1, 126.8, 126.5](Ph),62.3 (Cspir), 48.3 (OCH2), 31.5 (CPh2), 20.6 (CH2). IR (ATR) [cm-1]: ṽ = 2960, 2926, 2853, 1993, 1963, 1882, 1734, 1495, 1445, 1265, 1089, 1029, 1019, 852,15 801, 765, 700, 546, 525, 418. HR-MS-APCI(+) calc. C16H15O+ [M+H]+ 223.1118, found 223.1107.Synthesis of compound 10b 20 A solution of compound 9a (19.3 mg, 0.05 mmol) in C6D6 (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 80 oC for 12 h. All the volatiles were removed under reducedpressure, n-pentane (1 mL) was added into the solution with continuous stirring, during this time a colorlesssolid formed, which was collected by filtration and washed with cold n-pentane (1×0.5 mL) to givecompound 10b (16.3 mg, 0.046 mmol, 91%). Crystals of compound 10b suitable for X-ray diffraction were25 obtained from a solution of the colorless solid in ethyl acetate and pentane (ratio 1:10) at room temperature. Characterization data of compound 9a: 78 1H NMR (500 MHz, 298 K, C6D6): δ = [7.34, 7.27](each m, each 2H, m-C6H4), [7.07, 6.64](each m, each2H, o-C6H4), 2.73 (m, 2H, OCH2), [1.52, 1.44](each d, each 2JHH = 7.2 Hz, each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = [146.2, 144.6](i-C6H4), 129.8 (o-C6H4), [129.3, 129.0](each q,2JFC = 32.4 Hz, p-C6H4), [125.7, 125.6](each m, m-C6H4), [124.9, 124.8](each q, each 1JFC = 272.2 Hz, CF3),5 62.1 (Cspir), 48.1 (OCH2), 30.8 (C(Ar)2), 20.7 (CH2). IR (ATR) [cm-1]: ṽ = 2952, 2926, 1617, 1470, 1411, 1366, 1324, 1261, 1165, 1117, 1067, 1018, 1002, 908,858, 809, 750, 701, 681, 606, 527, 422. Synthesis of compound 11a 10 A solution of compound 9c (23.3 mg, 0.05 mmol) in C6D6 (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 80 oC for 12 h. All the volatiles were removed under reducedpressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compound 11a (19.7 mg, 0.045 mmol, 90%) as a colorless oil.15 Characterization data of compound 11a: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.35, 7.06](each m, each 2H, m-C6H4), 7.17 (s, 1H, CHb), [6.87,6.64](each m, each 2H, o-C6H4), 6.34 (s, 1H, CHa), 4.57 (m, 1H, CH), [3.30 (dd, 2JHH = 16.6 Hz, 4JHH = 1.2Hz), 2.96 (dd, 2JHH = 16.6 Hz, 4JHH = 2.5 Hz)](each 1H, CH2), 2.67 (s, 3H.3H).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 201.0 (C=O), [151.1, 146.1](i-C6H4), 138.5 (CHb), [129.3,20 129.1](each q, each 2JFC = 32.2 Hz, p-C6H4), 129.0 (CHa), [128.4, 127.9](o-C6H4), [125.8, 125.2](each q,3JFC = 3.7 Hz, m-C6H4), [124.8, 124.6](each q, each 1JFC = 272.2 Hz, CF3), 113.1 (i-C3N2), 66.1 (CH), 56.8(CH2), 44.8 (CAr2), 38.1 (CH3). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.2, -62.5. IR (ATR) [cm-1]: ṽ = 2964, 1782, 1617, 1411, 1323, 1260, 1165, 1118, 1067, 1016, 982, 902, 841, 800,25 774, 714, 668, 626, 605, 522. HR-MS-ESI(+) calc. C22H17F6N2O+ [M+H]+ 439.1240, found 439.1236. 79 Synthesis of compound 11b Asolution of compound 9d (23.4 mg, 0.05 mmol) in C6D6 (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 80 oC for 12 h. All the volatiles were removed under reduced5 pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compound 11b (20.5 mg, 0.046 mmol, 93%) as a colorless oil.Characterization data of compound 11b: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.34, 7.06](each m, each 2H, m-C6H4), [6.93, 6.65](each m, each10 2H, o-C6H4), [6.61, 6.53, 6.46](each m, each 1H, C4H3S), 4.81 (m, 1H, CH), [3.27 (dd, 2JHH = 17.0 Hz, 4JHH= 1.3 Hz), 2.88 (dd, 2JHH = 17.0 Hz, 4JHH = 2.4 Hz)](each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 199.3 (C=O), [150.8, 145.4](i-C6H4), [134.4, 127.6, 126.9,125.7](C4S), [129.4, 129.3](each q, 2JFC = 32.2 Hz, p-C6H4), [128.4, 127.9](o-C6H4), [125.8, 125.2](each q,3JFC = 3.8 Hz, m-C6H4), [124.8, 124.6](each q, 1JFC = 272.2 Hz, CF3), 68.9 (CH), 57.0 (CH2), 48.7 (CAr2).1519F NMR (470 MHz, 298 K, C6D6): δ = -62.2, -62.5. IR (ATR) [cm-1]: ṽ = 1788, 1617, 1411, 1324, 1241, 1166, 1119, 1069, 1016, 980, 904, 844, 773, 702, 615,515, 442. HR-MS-APCI(+) calc. C22H15F6OS+ [M+H]+ 441.0743, found 441.0721.Synthesis of compound 11c 20 Asolution of compound 9e (26.9 mg, 0.05 mmol) in C6D6 (0.5 mL) was transferred into a J-Young NMRtube. The reaction mixture was kept at 80 oC for 12 h. All the volatiles were removed under reducedpressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compound 11c (24.0 mg, 0.047 mmol, 94%) as a colorless oil.25 Characterization data of compound 11c: 80 1H NMR (500 MHz, 298 K, C6D6): δ = [7.38, 7.02](each m, each 2H, m-C6H4), [7.34 (2H), 7.26 (2H), 7.15(2H), 7.09 (1H), 6.90 (2H)](each m, Ph-C6H4), [6.95, 6.63](each m, each 2H, o-C6H4), 4.76 (m, 1H, CH),[3.38 (dd, 2JHH = 17.0 Hz, 4JHH = 1.2 Hz), 3.01 (dd, 2JHH = 17.0 Hz, 4JHH = 2.6 Hz)](each 1H, CH2).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 201.0 (C=O), [151.5, 145.7](i-C6H4), [141.0, 140.6, 132.6, 129.6,5 129.1, 127.7, 127.25, 127.23](Ph-C6H4), [129.3, 129.1](each q, each 2JFC = 32.2 Hz, p-C6H4), [128.7,127.9](o-C6H4), [125.9, 125.2](each q, each 3JFC = 3.8 Hz, m-C6H4), [124.8, 124.5](each q, 1JFC = 272.3 Hz,CF3), 73.3 (CH), 57.5 (CH2), 48.6 (CAr2). 19F NMR (470 MHz, 298 K, C6D6): δ = -62.2, -62.4. IR (ATR) [cm-1]: ṽ = 1783, 1616, 1488, 1410, 1323, 1261, 1165, 1118, 1068, 1016, 981, 908, 841, 757,10 732, 697, 636, 611, 547, 521, 437. HR-MS-APCI(+) calc. C30H21F6O+ [M+H]+ 511.1492, found 511.1480.Synthesis of compound 11d A solution of pyrene-1-carbaldehyde (11.5 mg, 0.05 mmol) in THF (0.5 mL) was added dropwise to a15 solution of compound 5j (27.1 mg, 0.05 mmol) in THF (0.5 mL) at room temperature. The reaction mixturewas stirred at 70 oC for 12 h. All the volatiles were removed under reduced pressure, the remaining residuewas purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 5:1) to give compounds 11d (12.5mg, 0.022 mmol, 45%) as a colorless solid. Crystals of compound 11d suitable for X-ray diffraction wereobtained from a solution of the colorless solid in ethyl acetate and n-pentane (ratio 1:10) at room20 temperature. Characterization data of compound 11d: 1H NMR (500 MHz, 298 K, C6D6): δ = [7.97, 7.91, 7.90, 7.85, 7.77, 7.74, 7.60, 7.51, 7.15](each m, each1H, pyrene), [7.34, 6.84](each m, each 2H, m-C6H4), [7.04, 6.52](each m, each 2H, o-C6H4), 5.90 (m, 1H,25 CH), [3.67 (d, 2JHH = 17.3 Hz), 3.27 (dd, 2JHH = 17.3, 4JHH = 2.7 Hz)](each 1H, CH2)13C{1H} NMR (125 MHz, 298 K, C6D6)[CF3 groups were not listed]: δ = 202.0 (C=O), [151.9, 144.2](i-C6H4),[131.7, 131.3, 130.9, 129.7, 129.4, 128.48, 128.46, 127.72, 127.67, 126.4, 126.2, 125.5, 125.4, 125.3, 124.7, 123.0](pyrene), [129.3, 127.6](o-C6H4), [125.9, 125.1](each q, each 3JFC = 3.8 Hz, m-C6H4), 72.6(CH), 57.3 (CH2), 50.3 (CAr2). 3019F NMR (470 MHz, 298 K, C6D6): δ = -62.1, -62.4. IR (ATR) [cm-1]: ṽ = 2963, 2928, 2853, 1786, 1617, 1411, 1325, 1260, 1167, 1121, 1070, 1016, 842, 820,800, 758, 716, 623, 602, 513, 463, 436. 81 HR-MS-APCI(+) calc. C34H21F6O+ [M+H]+ 559.1492, found 559.1481.Synthesis of compound 13a 5A solution of compound 12a (19.8 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at room temperature for 5 min. After the reaction wasstirred at room temperature for 30 min, all the volatiles were removed under reduced pressure, and the remaining residue was purified by column chromatography (eluent: n-pentane) to give 13a (15.1 mg, 0.072mmol, 72%) as a colorless solid. 10 Characterization data of compound 13a: Melting point 45.5 °C1H NMR (500 MHz, C6D6, 298 K) δ = 3.29 (s, 6H, OCH3), [2.81, 1.92](each m, each 2H, CH2c), [2.72, 1.80](each m, each 2H, CH2a).15 13C NMR (125 MHz, C6D6, 298 K) δ = 172.5 (C=O), 51.3 (OCH3), 51.0 (Cspir), 40.6 (Cc), 35.5 (Cb), 32.1 (Ca)IR [cm-1]: ṽ = 2988, 2958, 2929, 2853, 2044, 1708, 1431, 1406, 1315, 1281, 1216, 1191, 1166, 1114, 1068,1051, 1009, 897, 885, 871, 817, 781, 738, 699, 669, 616, 493, 438. HR-MS-ESI(+) m / z calcd. for C11H14NaN2O4 [M+Na]+ 233.0785, found 233.0785.20 Synthesis of compound 13a-13C Asolution of compound 12a (19.8 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3-13C (22.7 mg, 0.1 mmol) in THF (3.0 mL) at room temperature for 5 min. After the reactionwas stirred at room temperature for 30 min, all the volatiles were removed under reduced pressure. The25 remaining residue was purified by column chromatography (eluent: pentane) to give 13a-13C (15.1 mg, 0.072mmol, 72%) as a colorless solid. 1H NMR (500 MHz, C6D6, 298 K) δ = 3.30 (s, 6H, OCH3), [2.80, 1.92](each m, each 2H, CH2c), [2.72, 1.80](each m, each 2H, CH2a).30 13C NMR (125 MHz, C6D6, 298 K) δ = 172.5 (d, 2JCC =2.2 Hz, C=O), 51.3 (OCH3), 51.0 (Cspir), 40.6 (Cc),35.4 (d, 1JCC = 8.7 Hz, Cb), 32.1 (d, 1JCC = 28.1 Hz, Ca). 82 Synthesis of compound 13b Asolution of compound 12b (22.6 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at room temperature for 5 min. After the reaction was5 stirred at room temperature for 30 min, all the volatiles were removed under reduced pressure, the remaining residue was purified by column chromatography (eluent: n-pentane) to give 13b (16.4 mg, 0.069mmol, 69%) as a colorless oil. Characterization data of compound 13b: 101H NMR (500 MHz, C6D6, 298 K) δ = 3.93 (m, 2H, CH2Et), [2.87, 1.98](each m, each 2H, each CH2c), [2.78, 1.86](each m, each 2H, each CH2a), 0.91 (t, J = 7.1 Hz, 3H, CH3Et).13C NMR (125 MHz, C6D6, 298 K) δ = 172.1 (C=O), 60.3 (CH2Et), 51.0 (Cspir), 40.7 (CH2c), 35.6 (Cb), 32.0(CH2a), 14.4 (CH3Et). IR [cm-1]: ṽ = 2982, 2932, 1714, 1446, 1403, 1368, 1315, 1282, 1222, 1169, 1142, 1113, 1063, 1042, 1029,15 917, 861, 819, 742. HR-MS-ESI(+) m / z calcd. for C13H19O4 [M+H]+ 239.1278, found 239.1282.Synthesis of compound 13c 20 A solution of compound 12c (24.6 mg, 0.1 mmol) in C6D6 (0.3 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in C6D6 (0.3 mL) at room temperature for 5 min. After the reaction waskept at room temperature for 30 min, all the volatiles were removed under reduced pressure, n-pentane (1mL) was added into the solution with continuous stirring, during this time a colorless solid formed, which was collected by filtration and washed with cold n-pentane (1×1 mL) to give compound 13c (22.0 mg,25 0.085 mmol, 85%). Crystals of compound 13c suitable for X-ray diffraction were obtained from a solutionof the colorless solid in benzene at room temperature. Characterization data of compound 13c:Melting point 232.6 °C with decomposition.301H NMR (500 MHz, C6D6, 298 K) δ = 7.75 (m, 2H, 3-C6H4), 7.12 (m, 2H, 2-C6H4), 3.27 (s, 6H, OCH3), [2.84, 1.72](each d, each 2JHH = 4.7 Hz, each 2H, CH2a). 83 13C NMR (150 MHz, C6D6, 298 K) δ = 171.2 (C=O), 144.9 (1-C6H4), 129.1 (3-C6H4), 127.4 (2-C6H4), 51.5 (OCH3), 38.3 (Cspir), 37.0 (CH2b), 24.2 (CH2a). IR [cm-1]: ṽ = 2953, 1714, 1637, 1438, 1338, 1299, 1267, 1197, 1154, 1127, 1092, 954, 901, 815, 772, 708,672, 641, 548. 5HR-MS-APCI(+) m / z calcd. for C15H14NaO4 [M+Na]+ 281.0785; found 281.0781.Synthesis of compound 13d Asolution of compound 12d (17.9 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at room temperature for 5 min. After the reaction was10 stirred at room temperature for 30 min, all the volatiles were removed under reduced pressure, the remaining residue was purified by column chromatography (eluent: n-pentane) to give 13d (13.8 mg, 0.072mmol, 72%) as a colorless oil. Characterization data of compound 13d: 15 1H NMR (500 MHz, C6D6, 298 K) δ = 3.80 (q, 3JHH = 7.1 Hz, 2H, CH2Et), [2.53, 1.62](each m, each 1H,CH2c), [2.52, 1.80](each d, each m, CH2f), [1.89, 1.48](each m, each 1H, CH2a), [1.85, 1.68](each m, each 1H, CH2d), 0.81 (t, 3JHH = 7.1 Hz, 3H, CH3Et).13C NMR (125 MHz, C6D6, 298 K) δ = 171.0 (C=O), 120.7 (CN), 60.5 (CH2Et), 47.9 (Cspir), 42.7 (CH2d), 40.220 (CH2c), 35.4 (Cb), 31.5 (CH2f), 31.2 (CH2a), 18.7 (Ce), 14.2 (CH3Et). IR [cm-1]: ṽ = 2931, 2856, 2230, 1722, 1448, 1369, 1324, 1263, 1235, 1153, 1110, 1064, 1025, 854, 817,757. HR-MS-ESI(+) m / z calcd. for C11H14NO2 [M+H]+ 192.1019, found 192.1017.Synthesis of compound 13eOne pot reaction to synthesize compound 13e and 14e 25 Asolution of compound 12e (24.0 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) at -78 oC for 5 min. After the reaction was stirring at roomtemperature for 1 h, the solvent was changed to bromobenzene. The reaction mixture was heated at 12030oC for another 4 hours. All the volatiles were removed under reduced pressure, the remaining residue was purified by two times preparative TLC chromatography (eluent: n-pentane / EtOAc = 20:1) to give compound 13e(13.9 mg, 0.055 mmol, 55%) as a colorless oil. 84 Characterization data of compound 13e: 1H NMR (500 MHz, 298 K, C6D6): δ = 3.94 (m, 4H, CH2Et), [2.52, 1.00](each m, each 2H, CH2b), [2.22,1.04](each d, each 2JHH = 5.0 Hz, CH2a), 1.25 (m, 2H, CH2c), 0.91 (t, 3JHH = 7.1 Hz, CH3Et).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 173.5 (C=O), 60.3 (CH2Et), 31.2 (Cspir), 24.30 (CH2b), 24.27 (C),5 20.8 (CH2c), 20.5 (CH2a), 14.3 (CH3Et). IR (ATR) [cm-1]: ṽ = 2934, 2870, 1718, 1447, 1368, 1306, 1289, 1252, 1177, 1146, 1055, 1032, 863.HR-MS-ESI(+) calc. C14H20NaO4+ [M+Na]+ 275.1254, found 275.1251.Characterization data of compound 14e:10 1H NMR (500 MHz, 298 K, C6D6): δ = 5.02 (m, 1H, =CH2E), 4.82 (m, 1H, =CH2Z), 4.02 (m, 2H, CH2Et a), 3.96(m, 2H, CH2Et b), [3.64, 2.22](each m, each 1H, CH2a), [2.19, 1.96](each m, each 1H, CH2d), [2.19, 1.66](each m, each 1H, CH2b), [1.71, 1.64](each m, each 1H, CH2c), 1.00 (t, 3JHH = 7.1 Hz, CH3Et a), 0.97 (t,3JHH = 7.1 Hz, CH3Et b). 13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 174.0 (C=Oa), 171.4 (C=Ob), 147.1 (=C), 108.3 (=CH2), 67.815 (Cb), 60.6 (CH2Et a), 60.5 (CH2Et b), 53.6 (Ca), 37.4 (CH2a), 37.22 (CH2b), 37.17 (CH2d), 25.2 (CH2c), 14.2 (CH3Et a), 14.1 (CH3Et b). Synthesis of intermediate 15e 20 Step 1: A solution of compound 12e (24.0 mg, 0.1 mmol) in THF (0.5 mL) was added dropwise to a solutionof compound 3 (22.6 mg, 0.1 mmol) in THF (0.5 mL) at -78 oC for 5 min. After the reaction was stirring atroom temperature for 1 h, all the volatiles were removed under reduced pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 10:1) to give compound 15e (22.7mg, 0081 mmol, 81%) as a colorless solid.25 Step 2: A solution of compound 15e (14 mg, 0.05 mmol) in C6D5Br was transferred into a J-Young NMRtube. The solution was kept at 120 oC for 4 hours. The in situ 1H NMR shows a mixture of compound 13eand 14e (the ratio is ca. 2:1 with a total 93% NMR yield).Characterization data of compound 15e:30 1H NMR (500 MHz, 298 K, C6D6): δ = 4.02 (q, 3JHH = 7.1 Hz, 2H, CH2Et b), [3.79, 3.73](each m, each 1H,CH2Et a), [2.82, 1.89](each m, each 1H, CH2d), [2.72, 2.47](each d, 2JHH = 6.1 Hz, CH2a), [2.41, 1.08](eachd, 2JHH = 11.8 Hz, CH2e), [2.13, 1.36](each m, each 1H, CH2b), [1.89, 1.65](each m, each 1H, CH2c), 0.93(t, 3JHH = 7.1 Hz, 3H, CH3Et b ), 0.79 (t, 3JHH = 7.1 Hz, 3H, CH3Et a ).13C{1H} NMR (125 MHz, 298 K, C6D6): δ = 173.2 (C=Oa), 171.1 (C=Ob), 91.5 (Cb), 71.6 (Cspir), 61.5 (CH2Et35b), 61.1 (CH2Et a), 39.8 (CH2e), 36.6 (Ca), 34.8 (CH2d), 27.7 (CH2a), 22.2 (CH2c), 21.1 (CH2b), 14.0 (CH3Et). 85 IR (ATR) [cm-1]: ṽ = 2961, 2855, 1735, 1715, 1460, 1411, 1369, 1323, 1258, 1240, 1195, 1169, 1133, 1093,1066, 1026, 912, 864, 798, 601. HR-MS-ESI(+) calc. C14H20N2NaO4+ [M]+ 303.1316, found 303.1312.Synthesis of compound 13f 5One pot reaction to synthesis compound 13f and 14f Asolution of compound 12f (42.8 mg, 0.2 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3 (45.2 mg, 0.2 mmol) in THF (2.0 mL) at -78 oC for 5 min. After the reaction was stirring at roomtemperature for 1 h, the reaction mixture was heated at 70 oC for another 12 hours. All the volatiles were10 removed under reduced pressure, the remaining residue was purified by column chromatography (eluent: n-pentane / EtOAc = 4:1) to give 13f (12.6 mg, 0.056 mmol, 28%) as a colorless solid and compound 14f (27.6 mg,0.122 mmol, 61%) as a colorless solid. Characterization data of compound 13f:15 m.p.100.3 °C1H NMR (501 MHz, C6D6, 298 K) δ = [4.48, 2.91](each d, each 2JHH = 11.9 Hz, each 2H, each CH2a), 3.28(s, 6H, OCH3), [2.12, 1.08](each d, each 2JHH = 5.1 Hz, each 2H, each CH2c).13C NMR (126 MHz, C6D6, 298 K) δ = 172.3 (C=O), 64.8 (CH2a), 51.5 (OCH3), 28.5 (Cspir), 23.4 (Cb), 19.3 (CH2c).20 IR [cm-1]: ṽ = 2956, 2925, 2853, 1709, 1440, 1416, 1387, 1332, 1314, 1281, 1216, 1193, 1163, 1138, 1099,1078, 1066, 1047, 1028, 997, 931, 893, 876, 853, 806, 781, 755, 722, 589, 516, 491, 464, 444. HR-MS-APCI(+) m / z calcd. for C11H14NaO5 [M+Na]+ 249.0734; found 249.0737.Characterization data of compound 14f:25 m.p.104.0 °C1H NMR (500 MHz, C6D6, 298 K) δ [ppm] = [5.07, 4.83](each m, each 1H, each =CH2), [4.12, 3.97](each d, each 2JHH = 8.9 Hz, 1H, CH2f) [4.10, 3.81](each d, 2JHH = 9.2 Hz, 1H, CH2a), [3.38, 2.43](each, dt, 2JHH =16.7, 4JHH = 2.6 Hz, each 1H, CH2c), 3.36 (s, 3H, OCH3a), 3.24 (s, 3H, OCH3b).13C NMR (150 MHz, C6D6, 298 K) δ [ppm] = 171.4 (C=Oa), 169.3 (C=Ob), 144.9 (Cd), 109.4 (=CH2),30 76.8 (CH2f), 76.2 (CH2a), 68.2 (Ce), 54.7 (Cb), 51.7 (OCH3a), 51.6 (OCH3b), 36.8 (CH2c). IR [cm-1]: ṽ = 2953, 2920, 2850, 1732, 1679, 1436, 1293, 1258, 1196, 1172, 1134, 1097, 1068, 1048, 1015,935, 893, 798, 742, 723. HR-MS-APCI(+) m / z calcd. for C11H14NaO5 [M+Na]+ 249.0734; found 249.0736.35 Synthesis of intermediate 15f 86 Step 1: A solution of compound 12f (21.4 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solutionof compound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at -78 oC for 5 min. After the reaction was stirring at5 room temperature for 1 h, all the volatiles were removed under reduced pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 3:1) to give compound 15f (14.2mg, 0.056 mmol, 56%, with 82% NMR yield) as a colorless solid. Step 2: A solution of compound 15f (12.7 mg, 0.025 mmol) in C6D6 (0.5 mL) was transferred into a J-YoungNMR tube. The solution was kept at 70 oC for 12 hours. The in situ 1H NMR spectrum shows a mixture of10 compound 13f and 14f (the ratio is ca. 2:5 with a total 94% NMR yield).Characterization data of compound 15f: m.p.83.1 °C1H NMR (600 MHz, C6D6, 298 K) δ = [4.63, 3.83](each d, each 2JHH = 14.2 Hz, each 1H, each CH2g), [4.42,15 3.06](each d, each 2JHH = 11.8 Hz, each 2H, each 1H, each CH2a), 3.30 (s, 3H, OCH3b), [3.21, 1.05](eachd, each 2JHH = 6.9 Hz, each 1H, CH2c), 3.21(s, 3H, OCH3a), [1.88, 1.80](each d, each 2JHH = 12.5 Hz,each 1H, each CH2e). 13C NMR (151 MHz, C6D6, 298 K) δ = 170.5 (C=Ob), 169.9 (C=Oa), 91.6 (Cf), 78.0 (Cd), 71.8 (CH2a), 70.7 (CH2g), [52.29, 52.26](each OCH3), 39.2 (Cb), 34.4 (CH2e), 27.0 (CH2c).20 IR [cm-1]: ṽ = 2961, 1721, 1437, 1379, 1308, 1266, 1243, 1226, 1211, 1156, 1104, 1080, 1053, 1036, 1017,975, 966, 948, 879, 853, 838, 780, 733, 712, 702, 683, 630, 526, 484, 473, 425. HR-MS-APCI(+) m / z calcd. for C11H14N2NaO5 [M+Na]+ 277.0795; found 277.0798.Synthesis of compound 13g One pot reaction to synthesis compound 13g 25 Asolution of compound 12g (51.6 mg, 0.2 mmol) in THF (0.5 mL) was added dropwise to a solution ofcompound 3 (45.2 mg, 0.2 mmol) in THF (0.5 mL) at -78 oC for 5 min. After the reaction was stirring at roomtemperature for 1 h, the solvent was changed to bromobenzene. The reaction mixture was heated at 120 oC for another 4 hours. All the volatiles were removed under reduced pressure, the remaining residue was 87 purified by two times preparative TLC chromatography (eluent: n-pentane / EtOAc = 5:1) to give compound 13g(28.6 mg, 0.106 mmol, 53%) as a colorless oil. Characterization data of compound 13g: 51H NMR (501 MHz, C6D6, 298 K) δ = 3.92 (m, 4H, CH2Et), [3.62, 1.94](each d, each 2JHH = 13.7 Hz, each2H, CH2a), [2.05, 1.09](each d, each 2JHH = 4.8 Hz, each 2H, CH2c), 0.90 (t, 3JHH = 7.1 Hz, 6H, CH3Et).13C NMR (126 MHz, C6D6, 298 K) δ = 172.2 (C=O), 60.8 (CH2Et), 31.6 (Cspir), 27.8 (CH2a), 23.7 (Cb), 19.2 (CH2c), 14.2 (CH3Et). IR [cm-1]: ṽ = 2982, 2930, 1719, 1466, 1368, 1326, 1298, 1259, 1224, 1180, 1147, 1112, 1030, 864, 761,10 662. HR-MS-APCI(+) m / z calcd. for C13H18NaO4S [M+Na]+ 293.0818; found 293.0806.Synthesis of intermediate 15g 15 Step 1: A solution of compound 12g (25.8 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solutionof compound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at -78 oC for 5 min. After the reaction was stirring atroom temperature for 1 h, all the volatiles were removed under reduced pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 3:1) to give compound 15g (24.7mg, 0.083 mmol, 83%) as a colorless solid.20 Step 2: A solution of compound 15g (14.9 mg, 0.025 mmol) in C6D6 (0.5 mL) was transferred into a J-YoungNMR tube. The solution was kept at 120 oC for 12 hours. The in situ 1H NMR spectrum shows a mixture ofcompound 13g (61% NMR yield) and other unidentified compounds.Characterization data of compound 15g:25 1H NMR (600 MHz, C6D6, 298 K) δ = 3.94 (q, 3JHH = 7.1 Hz, 2H, CH2Et a), [3.88, 3.76](each m, each 1H,CH2Et b), [3.81 (m), 3.09 (d, 2JHH = 15.3 Hz)](each 1H, CH2g), [3.13 (m), 2.54 (d, 2JHH = 11.1 Hz)](each 1H,CH2a), [2.61, 2.22](each d, each 2JHH = 6.2 Hz, each 1H, CH2c), [2.38 (m), 2.13 (d, 2JHH = 12.2 Hz)](each1H, CH2e), [0.871, 0.868](each t, each 3JHH = 7.1 Hz, CH3Et).13C NMR (151 MHz, C6D6, 298 K) δ = 171.4 (C=Oa), 169.9 (C=Ob), 90.4 (Cf), 72.6 (Cd), 62.0 (CH2Et a), 61.730 (CH2Et b), 39.0 (CH2e), 38.3 (CH2g), 36.7 (Cb), 28.6 (CH2c), 28.2 (CH2a), [14.0, 13.9]( CH3Et). IR [cm-1]: ṽ = 2972, 2857, 1718, 1462, 1368, 1307, 1261, 12412, 1198, 1160, 1066, 1021, 908, 863, 800,742, 695, 660. HR-MS-APCI(+) m / z calcd. for C13H18N2NaO4S [M+Na]+ 321.0879; found 321.0868.Synthesis of compound 13h (trans-13h and cis-13h)35 One-pot reaction to synthesis compound trans-13h and 14h 88 Asolution of compound 12h (110.1 mg, 0.3 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3 (67.8 mg, 0.3 mmol) in THF (5.0 mL) at -78 oC for 5 min. After the reaction was stirring at roomtemperature for 1 h, the reaction mixture was heated at 70 oC for another 12 hours. All the volatiles were5 removed under reduced pressure, the remaining residue was purified by column chromatography (eluent: n- pentane / EtOAc = 3:1) to give compound trans-13h (17.0 mg, 0.045 mmol, 15%) as a colorless solid andcompound 14h (85.3 mg, 0.225 mmol, 75%) as a colorless solid.Crystals of compound trans-13h suitable for X-ray diffraction were obtained from a solution of the colorlesssolid in ethyl acetate and pentane (ratio 1:3) at room temperature.10 Crystals of compound 14h suitable for X-ray diffraction were obtained from a solution of the colorless solidin ethyl acetate and pentane (ratio 1:3) at room temperature. Characterization data of compound trans-13h:m.p.145.1 °C15 1H NMR (501 MHz, C6D6, 298 K) δ = 7.70 (m, 2H, o-C6H4), 6.77 (m, 2H, m-C6H4), [4.16, 2.55](each d,each 2JHH = 12.6 Hz, each 2H, each CH2a), 3.28 (s, 6H, OCH3), [1.99, 1.03](each d, each 2JHH = 5.2 Hz,each 2H, each CH2c), 1.87 (s, 3H, CH3). 13C NMR (126 MHz, C6D6, 298 K) δ = 171.7 (C=O), 143.0 (p-C6H4), 135.1 (i-C6H4), 129.7 (m-C6H4), 128.1 (o-C6H4), 51.7 (OCH3), 45.4 (CH2a), 29.2 (Cspir), 24.3 (Cb), 21.0 (CH3), 20.6 (CH2c).20 IR [cm-1]: ṽ = 2966, 2923, 2134, 1992, 1717, 1598, 1494, 1478, 1433, 1414, 1390, 1353, 1337, 1312, 1275,1193, 1163, 1140, 1117, 1090, 1034, 1008, 977, 949, 932, 894, 877, 858, 835, 814, 801, 770, 754, 711, 684, 652, 593, 550, 500, 439. HR-MS-APCI(+) m / z calcd. for C18H21NNaO6S [M+Na]+ 402.0982; found 402.1001.25 Characterization data of compound 14h:m.p.134.9 °C.1H NMR (501 MHz, C6D6, 298 K) δ = 7.67 (m, 2H, o-C6H4), 6.70 (m, 2H, m-C6H4), 5.05 (m, 1H, =CH2Z),4.82 (m, 1H, =CH2E), [4.01, 3.21](each d, each 2JHH = 9.6 Hz, each 1H, each CH2f), [3.66, 3.28](each d,each 2JHH = 9.8 Hz, each 1H, each CH2a), [3.35, 2.55](each dt, each 2JHH = 16.9 Hz, 3JHH = 2.6 Hz,30 each 1H, each CH2c), 3.18 (s, 3H, OCH3a), 3.10 (s, 3H, OCH3b), 1.81 (s, 3H, CH3). 13C NMR (126 MHz, C6D6, 298 K) δ = 171.0 (C=Oa), 169. 1 (C=Ob), [143.54, 143.50](Cd, p-C6H4), 132.7 (i-C6H4), 129.7 (m-C6H4), 128.3 (o-C6H4), 110.5 (=CH2), 65.8 (Ce), 57.0 (CH2f), 56.5 (CH2a), 53.0 (Cb), 51.83 (OCH3a), 51.78 (OCH3b), 37.1 (CH2c), 21.1 (CH3) IR [cm-1]: ṽ = 2923, 2853, 1733, 1680, 1598, 1457, 1437, 1353, 1257, 1167, 1135, 1090, 1067, 1049, 1006,35 906, 815, 800, 752, 733, 709, 662, 612, 584, 550, 480. HR-MS-APCI(+) m / z calcd. for C18H21NNaO6S [M+Na]+ 402.0982; found 402.0983. 89 Synthesis of intermediate 15h Step 1: A solution of compound 12h (36.7 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solutionof compound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at -78 oC for 5 min. After the reaction was stirring at5 room temperature for 1 h, all the volatiles were removed under reduced pressure, the remaining residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 2:1) to give compound 15h (35.8mg, 0.088 mmol, 88%) as a colorless solid. Crystals of compound 15h suitable for X-ray diffraction wereobtained from a solution of the colorless solid in ethyl acetate and n-pentane (ratio 1:2) at room temperature.10 Step 2: A solution of compound 15h (10.2 mg, 0.025 mmol) in C6D6 (0.5 mL) was transferred into a J-YoungNMR tube. The solution was kept at 70 oC for 12 hours. The in situ 1H NMR spectrum shows a mixture ofcompound trans-13h and compound 14h (the ratio is ca. 1:5 with a total 90% NMR yield).Characterization data of compound 15h:15 m.p.133.6 °C.1H NMR (501 MHz, C6D6, 298 K) = 7.70 (m, 2H, o-C6H4), 6.74 (m, 2H, m-C6H4), [5.15, 2.83](each d,each 2JHH = 16.1 Hz, each 1H, CH2g), [3.82, 3.08](each d, each 2JHH = 12.5 Hz, each 1H, CH2a), 3.41 (s,3H, OCH3b), [3.07, 0.86](each d, each 2JHH = 7.1 Hz, each 1H, CH2c), 2.95 (s, 3H, OCH3a), [1.98,1.67](each d, each 2JHH = 13.2 Hz, each 1H, CH2e), 1.84 (s, 3H, CH3).2013C NMR (126 MHz, C6D6, 298 K) δ = 169.8 (C=Ob), 169.0 (C=Oa), 143.0 (p-C6H4) 137.1 (i-C6H4), 129.7 (m- C6H4), 127.3 (o-C6H4), 90.9 (Cf), 76.1 (Cd), 52.8 (OCH3b), 52.2 (OCH3a), 51.9 (CH2a), 51.10 (CH2g), 34.6 (CH2e), 32.9 (Cb), 25.5 (CH2c), 21.0 (CH3). IR [cm-1]: ṽ = 1739, 1713, 1438, 1342, 1291, 1264, 1245, 1222, 1160, 1125, 1107, 1091, 1039, 1000, 898,877, 856, 831, 806, 792, 770, 708, 669, 639, 624, 545, 493, 427.25 HR-MS-APCI(+) m / z calcd. for C18H21N3NaO6S [M+Na]+ 430.1043; found 430.1040.Synthesis of compound cis-13h (irradiation of intermediate 15h) Asolution of compound 15h (20.4 mg, 0.05 mmol) in C6D6 (0.5 mL) was transferred into a quartz J-Young30 NMR tube. The reaction mixture was irradiated under 370 nm blue light for 12 h. The reaction was monitored by 1H NMR until the reaction finished. All the volatiles were removed under reduced pressure, the remaining 90 residue was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 3:1) to give compound cis-13h (15.3 mg, 0.041 mmol, 81%) as a colorless solid. Crystals of compound cis-13h suitable for X-raydiffraction were obtained from a solution of the colorless solid in ethyl acetate and n-pentane (ratio 1:2) atroom temperature. 5 Characterization data of compound cis-13h:1H NMR (501 MHz, C6D6, 298 K) = 7.72 (m, 2H, o-C6H4), 6.73 (m, 2H, m-C6H4), [4.54, 3.06](each d, each2JHH = 12.8 Hz, each 1H, CH2a), [4.46, 3.09]( each d, each 2JHH = 10.4 Hz, each 1H, CH2a), [3.22, 2.82](eachs, each 3H, OMe), [2.75, 1.81](each d, each 2JHH = 5.1 Hz, each 1H, CH2b’), 1.86 (s, 3H, Me), [1.37,10 1.21](each d, each 2JHH = 4.6 Hz, each 1H, CH2b).13C NMR (126 MHz, C6D6, 298 K) δ = [173.5, 170.9](C=O), 142.4 (p-C6H4), 137.6 (i-C6H4), 129.6 (m-C6H4), 127.3 (o-C6H4), [51.6, 51.5](OMe), 50.4 (CH2a’), 45.6 (CH2a), 34.0 (Cc), 33.5 (CH2b’), 32.8 (Cspir), 24.5 (Cc’), 21.0 (Me), 14.9 (CH2b). IR [cm-1]: ṽ = 3358, 2954, 2920, 2850, 1724, 1659, 1632, 1598, 1494, 1437, 1400, 1351, 1298, 1252, 1205,15 1163, 1133, 1111, 1085, 1019, 980, 940, 885, 844, 816, 784, 745, 708, 669, 557. HR-MS-APCI(+) m / z calcd. for C18H21NNaO6S [M+Na]+ 402.0982; found 402.1001.Synthesis of compound 13i One pot reaction to synthesis compound 13i and 14i 20 A solution of compound 12i (34.8 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solution ofcompound 3 (22.6 mg, 0.1 mmol) in THF (2.0 mL) at -78 oC for 5 min. After the reaction was stirred at roomtemperature for 1 h, the reaction mixture was heated at 70 oC for another 12 hours. All the volatiles wereremoved under reduced pressure, the remaining residue was purified by column chromatography (eluent: n-pentane / EtOAc = 3:1) to give 13i (12.6 mg, 0.035 mmol, 35%) as a colorless solid and compound 14i (16.2 mg,25 0.045 mmol, 45%) as a colorless solid. Characterization data of compound 13i: 1H NMR (501 MHz, C6D6, 298 K) δ = 7.59 (m, 2H, o-C6H4), 6.78 (m, 2H, m-C6H4), [4.07, 2.31](each d,each 2JHH = 12.9 Hz, each 1H, each CH2f), 3.83 (m, 2H, CH2Et), [3.25, 2.43](each d, each 2JHH = 12.9 Hz,30 each 1H, each CH2a), 1.88 (s, 3H, CH3), [1.71, 1.00](each d, each 2JHH = 5.4 Hz, each 1H, each CH2d),[1.45, 0.87](each d, each 2JHH = 6.0 Hz, 1H, CH2c), 0.89 (t, 3JHH = 7.2 Hz, 3H, CH3Et).13C NMR (126 MHz, C6D6, 298 K) δ = 170.3 (C=O), 143.5 (p-C6H4), 135.1 (i-C6H4), 129.8 (m-C6H4), 128.0 (o-C6H4), 120.1 (CN), 61.3 (CH2Et), 46.2 (CH2a), 45.0 (CH2f), 26.8 (Cspir), 24.0 (Ce), 21.0 (CH3), 19.5 (CH2d), 18.7 (CH2c), 14.0 (CH3Et), 10.7 (Cb).35 IR [cm-1]: ṽ = 2958, 2927, 2855, 2283, 1726, 1598, 1463, 1354, 1341, 1265, 1165, 1118, 1091, 1043, 1021,997, 929, 900, 842, 817, 778, 722, 665, 567, 549. 91 HR-MS-APCI(+) m / z calcd. for C18H21N2O4S [M+H]+ 361.1217; found 361.1215.Characterization data of compound 14i:1H NMR (501 MHz, C6D6, 298 K) δ = 7.55 (m, 2H, o-C6H4), 6.71 (m, 2H, m-C6H4), 4.89 (m, 1H, =CH2Z),5 4.65 (m, 1H, =CH2E), [3.91, 3.82](each m, each 1H, CH2Et), [3.84, 3.09](each d, each 2JHH = 10.0 Hz, each1H, CH2f), [3.43, 2.71](each d, each 2JHH = 10.1 Hz, each 1H, CH2a), [2.78, 2.36](each dt, each 2JHH = 17.1,4JHH = 2.7 Hz, each 1H, each CH2c), 1.85 (s, 3H, CH3), 0.90 (t, 3JHH = 7.1 Hz, 3H, CH3Et).13C NMR (126 MHz, C6D6, 298 K) δ = 167.3 (C=O), 143.9 (p-C6H4), 141.4 (Cd), 132.5 (i-C6H4), 129.8 (m-C6H4), 128.1 (o-C6H4), 118.2 (CN), 111.3 (=CH2), 65.7 (Ce), 62.1 (CH2Et), 56.4 (CH2f),10 56.1 (CH2a), 39.8 (Cb), 39.0 (CH2c), 21.1 (CH3), 13.8 (CH3Et). IR [cm-1]: ṽ = 2958, 2927, 2854, 2241, 2212, 2015, 1731, 1597, 1468, 1456, 1355, 1261, 1169, 1110, 1093,999, 911, 815, 709, 663, 626, 563, 549. HR-MS-APCI(+) m / z calcd. for C18H20N2NaO4S [M+Na]+ 383.1036; found 383.1032.15 Synthesis of intermediate 15i Step 1: A solution of compound 12i (34.8 mg, 0.1 mmol) in THF (1.0 mL) was added dropwise to a solutionof compound 3 (22.6 mg, 0.1 mmol) in THF (3.0 mL) at -78 oC for 5 min. After the reaction was stirring atroom temperature for 1 h, all the volatiles were removed under reduced pressure, and the remaining residue20 was purified by silica gel column chromatography (eluent: n-pentane / EtOAc = 2:1) to give compound 15i (31.1mg, 0.080 mmol, 80%) as a colorless solid. Step 2: A solution of compound 15i (9.7 mg, 0.025 mmol) in C6D6 (0.5 mL) was transferred into a J-YoungNMR tube. The solution was kept at 70 oC for 12 hours. The in situ 1H NMR spectrum shows a mixture ofcompound 13i and 14i (the ratio is ca. 5:6 with a total 95% NMR yield).25 Characterization data of compound 15i: 1H NMR (501 MHz, C6D6, 298 K) δ = 7.56 (m, 2H, o-C6H4), 6.73 (m, 2H, m-C6H4), [4.91, 2.70](each d,each 2JHH = 16.5 Hz, each 1H, each CH2g), 4.06 (m, 2H, CH2Et), [3.47, 2.92](each d, each 2JHH = 13.2 Hz,each 1H, each CH2a), [2.08, 0.66](each d, each 2JHH = 7.8 Hz, each 1H, each CH2c), [1.89, 1.39](each d,30 each 2JHH = 13.5 Hz, each 1H, each CH2e), 1.85 (s, 3H, CH3), 0.99 (t, 3JHH = 7.1 Hz, 3H, CH3Et).13C NMR (126 MHz, C6D6, 298 K) δ = 168.5 (C=O), 143.9 (p-C6H4), 136.2 (i-C6H4), 130.0 (m-C6H4), 127.1 (o-C6H4), 117.7 (CN), 91.6 (Cf), 72.0 (Cd), 62.5 (CH2Et), 51.8 (CH2a), 50.5 (CH2g), 33.1 (CH2e), 26.0 (CH2c), 21.1 (CH3), 17.0 (Cb), 14.1 (CH3Et). IR [cm-1]: ṽ = 2253, 1737, 1597, 1491, 1444, 1392, 1366, 1343, 1304, 1240, 1157, 1124, 1104, 979, 927,35 898, 884, 859, 816, 800, 776, 757, 707, 667, 623, 558, 546, 431. HR-MS-APCI(+) m / z calcd. for C18H20N4NaO4S [M+Na]+ 411.1098; found 411.1091. 92 Scaled-up experiment for synthesis of compound 1a [Ph2SCH3][OTf] (25.0 g, 71.35 mmol, 2.20 equiv) was dissolved in THF (250 ml) and cooled down to -78 °C. 5In another Schlenktube, n-BuLi (44.60 ml, 71.35 mmol, 2.20 equiv, 1.6 M in hexane,) was dissolved in thf(50 ml) and cooled down to -78 °C as well. The light-yellow n-BuLi solution was added dropwise at -78 °Cfor 15 min to the white suspension of the sulfonium salt, resulting in a yellow solution. Triphenylphosphine dichloride (10.81 g, 32.43 mmol, 1 equiv) was added to another different Schlenktube and THF (100 ml) was added. The white suspension was then cooled down to -78 °C and added to the yellow solution at -10 78 °C. After complete addition the yellow reaction mixture was slowly warmed up to room temperature and stirred for 2 h. During the reaction time the yellow colour lightens up. Then the solvent was removed under reduced pressure and the formed white solid residue was extracted with CH2Cl2 (3x 100 ml) and filtered over a celite-pad. The CH2Cl2 solution was concentrated by removing the solvent under reduced pressure. Et2O was added to precipitate the product 1a (16.07 g, 26.32 mmol, 81%), which was obtained as a white15 solid after filtration and drying under reduced pressure. The filtrate was put at 6 °C over 2 days to crystallize more of the product 1a (1.0 g, 5%) to obtain a total yield of 86%.Scaled-up experiment for synthesis of compound 13a 20 Two 120 mL pressure Schlenk flasks were charged with a mixture of 1a (2.00 g, 3.28 mmol, in total1.30 equiv.) and KHMDS (629 mg, 3.15 mmol, in total 1.25 equiv.) in a nitrogen filled glovebox. To each flask was added THF (60 mL) at –78 °C at an argon Schlenk-line. The intense yellow suspension was stirred for two hours at the same temperature. After degassing the solution under vacuum at −78 °C, nitrous oxide (1.0 bar) was introduced, and the flask was sealed. The mixture was then slowly warmed to room25 temperature over 90 minutes under exclusion of light. The residual gas pressure of both reaction flasks was vented and the atmosphere replaced with argon. Both solutions were unified in one Schlenk flask by cannula transfer. The yellow solution was cooled back to −78 °C, and a solution of 12a (1.00 g, 5.04 mmol,1.00 equiv.) in THF (20 mL) was added dropwise via cannula transfer. The mixture was stirred for 10 minutes at −78 °C before being allowed to warm to room temperature, and was subsequently stirred for 1230 hours. The reaction was quenched by the addition of two drops of water, and the resulting mixture was evaporated onto 10 g of silica gel prior to purification by automatic flash column chromatography (Machine: Interchim PuriFlash 5.020, column: Büchi GlassPure 26 mm x 230 mm, 60 ml / min, Cy: EtOAc, 100% → 98% 2min, 98% → 95% 15 min, 95% 30min). The product fraction (17–24 min, rf 0.3 in 10:1 Cy: EtOAc) 93 was collected based on TLC stained with KMnO4 solution. The fractions were unified and the test tubes rinsed with CH2Cl2. After evaporation 13a (862 mg, 4.10 mmol, 81%) was obtained as a colorless oil thatsolidified upon standing at 4 °C for 30 min. 5 Scaled-up experiment for synthesis of compound 15h A120 mL pressure Schlenk flask was charged with a mixture of 1a (1.60 g, 262 mmol. 1.30 equiv.) andKHMDS (504 mg, 2.53 mmol, 1.25 equiv.) in a nitrogen filled glovebox. THF (60 mL) was added at –78 °C at an argon Schlenk-line. The mixture was stirred at this temperature for two hours, resulting in the formation10 of an intense yellow solution. After degassing the solution under vacuum at −78 °C, nitrous oxide (1.0 bar) was introduced, and the flask was sealed. The mixture was then slowly warmed to room temperature over 90 minutes under exclusion of light. The resulting light orange mixture was cooled back to −78 °C, and a solution of 12h (687 mg, 1.87 mmol, 1.00 equiv.) in THF (10 mL) was added dropwise. The mixture wasstirred for 10 minutes at −78 °C before being allowed to warm to room temperature, and was subsequently15 stirred for 10 hours. The reaction was quenched by the addition of two drops of water, and the resulting mixture was evaporated onto 5 g of silica gel prior to purification by automatic flash column chromatography (Machine: Interchim PuriFlash 5.020, column: Büchi GlassPure 26 mm x 230 mm, 60 ml / min, Cy: EtOAc 100% → 98% 2min, 25 min 98% → 66%). The product fraction (7–14 min; rf: 0.49, 2:1 Cy: EtOAc) was collected based on TLC stained with KMnO4 solution. The fractions were unified and the test tubes rinsed20 with CH2Cl2. After evaporation 15h (516 mg, 1.27 mmol, 67%) was obtained as a colorless solid.Scaled-up experiment for synthesis of compound 7e A120 mL pressure Schlenk flask was charged with a mixture of 1a (1.60 g, 262 mmol. 1.30 equiv.) and25 KHMDS (504 mg, 2.53 mmol, 1.25 equiv.) in a nitrogen filled glovebox. THF (60 mL) was added at –78 °C at an argon Schlenk-line. The mixture was stirred at this temperature for two hours, resulting in the formation of an intense yellow solution. After degassing the solution under vacuum at −78 °C, nitrous oxide (1.0 bar) was introduced, and the flask was sealed. The mixture was then slowly warmed to room temperature over 90 minutes under exclusion of light. To the resulting light orange mixture was added a solution of freshly30 dried (CaH2) and distilled methylmethacrylate (202 mg, 2.02 mmol, 1.00 equiv.) in THF (10 mL) dropwise over 5 minutes. The reaction mixture was stirred for 2 hours, before dimethylfumerate (436 mg, 3.03 mmol, 94 1.50 equiv.) in THF (10 mL) was added. The resulting orange solution was stirred at 50 oC for 12 hours.The reaction was quenched by the addition of two drops of water, and the resulting mixture was evaporated onto 5 g of silica gel prior to purification by automatic flash column chromatography (Machine: Interchim PuriFlash 5.020, column: Büchi GlassPure 26 mm x 230 mm, 60 ml / min, Cy: EtOAc 20% 10 min, 20% → 5 33% 25 min). The product fraction (9.30–19 min; rf: 0.33, 2:1 Cy: EtOAc) was collected based on TLC stained with KMnO4 solution. The fractions were unified and the test tubes rinsed with CH2Cl2. After evaporation 7e (561 mg, 1.97 mmol, 97%, dr: 5:4) was obtained as a colorless solid.Scaled-up experiment for synthesis of compound 8e 10 7e (540 mg, 1.90 mmol, 1.0 equiv.) was dissolved in 7 ml Bromobenzene and heated to 130 °C. The reaction was monitored by NMR spectroscopy until full completion was reached (15 hours). The solvent was removed under reduced pressure to furnish 8e (413 mg, 1.61 mmol, 85%, dr: 1:1) as a light-yellow oil.Synthesis of compound 13aI 15 To a clear colorless solution of the diester 13a (0.050 g, 0.238 mmol, 1.0 equiv) in THF (5 mL) was addedlithium aluminum hydride (0.018 g, 0.474 mmol, 2.0 equiv) at 0 °C. After being stirred for 40 min at 0 °C, the grey turbid suspension was diluted by the addition of a saturated aqueous NH4Cl solution (5 mL) and a saturated aqueous potassium sodium tartrate solution (10 ml). The resultant biphasic solution was then20 vigorously stirred at room temperature overnight. The phases were separated, and the aqueous layer was extracted five times with EtOAc (30 mL). The combined organic layers were dried (Na2SO4) and silica gel was added. After removal of all volatiles under reduced pressure the resultant powdery white solid was loaded onto a silica gel column. Purification by silica gel column chromatography (cyclohexane‒ethyl acetate, 10:1 to 5:1 to 2:1 to 0:1) afforded the diol 13aI (0.0335 g, 0.217 mmol, 91%) as a colorless oil. Rf25 = 0.4 (ethyl acetate). Characterization data of compound 13aI: 1H NMR (500 MHz, CDCl3, 298 K) δ = [3.66, 3.46](each d, each 2JHH = 11.2 Hz, each 2H, CH2OH), [2.13,2.06](each m, each 2H, CH2c), 1.74 (m, 4H, CH2a), 1.29 (br, 2H, OH).30 13C NMR (125 MHz, CDCl3, 298 K) δ = 67.0 (CH2OH), 41.4 (CH2c), 37.3 (Cspir), 32.3 (Cb), 27.0 (CH2a).IR [cm-1]: ṽ = 3311, 3038, 2935, 2853, 1438, 1367, 1249, 1185, 1095, 1038, 972, 920, 864, 820, 748, 705,591, 537, 474, 453. 95 HR-MS-ESI(+) m / z calcd. for C9H15O2 [M+H]+ 155.1067, found 155.1067.Stability monitoring of compound 13aIin C6D6solution To a CDCl3 (0.6 mL) solution of compound 13aI (4.1 mg, 0.027 mmol) was added 1,3,5-trimethoxybenzene(1.9 mg, 0.011 mmol) as internal standard. The solution was transferred to a J-Young NMR tube and heated5 at 80 oC which was monitored by 1H NMR experiments. Figure S283 shows the time dependentdecomposition of 13aI.Synthesis of compound 13aII To a clear colorless solution of the diester 13a (0.210 g, 0.999 mmol, 1.0 equiv) in THF (20 mL) a sodium10 hydroxide solution (2.18 M in MeOH, 0.48 mL, 1.046 mmol, 1.05 equiv) was added dropwise at room temperature. After being stirred for 17 h at room temperature, the white suspension was concentrated under reduce pressure to give a white solid. The residue was dissolved in water (20 ml) and extracted three times with CH2Cl2 (30 ml). Subsequently, the aqueous layer was acidified to pH = 2 using conc. hydrochloric acid and extracted five times with CH2Cl2 (30 ml). The combined organic layers were dried (Na2SO4) and15 concentrated under reduced pressure to give the compound 13aII (0.1913 g, 0.975 mmol, 98%) as a whitesolid. Rf 0.64 (ethyl acetate). Characterization data of compound 13aII: 1H NMR (500 MHz, CDCl3, 298 K)[COOH was not listed] δ = 3.67 (s, 3H, OMe), [2.84, 2.18](each m, each20 1H, CH2f), [2.79, 2.16](each m, each 1H, CH2a), [2.76, 2.10](each m, each 1H, CH2c), [2.73, 2.07](each m, each 1H, CH2d). 13C NMR (125 MHz, CDCl3, 298 K) δ = 179.3 (COOH), 173.4 (C=O), 52.22 (Cspir), 52.17 (OMe), 40.7 (CH2c),40.0 (CH2d), 35.4 (Ce), 35.2 (Cb), 33.2 (CH2f), 32.4 (CH2a). IR [cm-1]: ṽ = 2927, 2854, 1714, 1672, 1436, 1325, 1291, 1235, 1207, 1175, 1151, 1118, 1069, 1044, 1001,25 962, 909, 883, 821, 540. HR-MS-ESI(+) m / z calcd. for C10H13O4 [M+H]+ 197.0808, found 197.0807.Synthesis of compound 13aIII To a clear colorless solution of the compound 13aII (0.1 g, 0.510 mmol, 1.0 equiv) in CH2Cl2 (10 mL)30 pyrrolidine (0.06 mL, 0.052 g, 0.715 mmol, 1.4 equiv), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide 96 (0.156 g, 0.813 mmol, 1.6 equiv) and 4-dimethylaminopyridine (0.014 g, 0.102 mmol, 0.2 equiv) were added sequentially at room temperature. After being stirred for 16 h at room temperature, the reaction mixture was diluted with a saturated aqueous NH4Cl solution (20 mL). The phases were separated and the aqueous layer was extracted four times with EtOAc (30 mL). The combined organic layers were dried (Na2SO4) and 5 silica gel was added. After removal of all volatiles under reduced pressure the resultant powdery white solid was loaded onto a silica gel column. Purification by silica gel column chromatography (cyclohexane‒ethyl acetate, 5:1 to 1:1 to 0:1) afforded the amide 13aIII (0.1027 g, 0.217 mmol, 81%) as a white solid. Rf 0.41(ethyl acetate). 10 Characterization data of compound 13aIII: 1H NMR (500 MHz, CDCl3, 233 K) δ = 3.64 (s, 3H, OMe), [3.56 (1H), 3.40 (2H), 3.35(1H)](each m, CH2g), [2.79, 2.66](each m, each 1H, CH2a), [2.69, 2.11](each m, each 1H, CH2c), 2.28 (m, 2H, CH2d), [2.06, 1.92](each m, each 1H, CH2f), 1.88 (m, 4H, CH2h). 13C NMR (125 MHz, CDCl3, 233 K) δ = 174.8 (OC=O), 171.1 (NC=O), 52.2 (OMe), [47.3, 45.7](CH2g), 46.615 (Cspir), 42.8 (CH2d), 39.1 (CH2c), 34.4 (Ce), 33.4 (Cb), 32.6 (CH2a), 28.9 (CH2f), [26.1, 24.4](CH2h). IR [cm-1]: ṽ = 2952, 2873, 1715, 1629, 1425, 1318, 1282, 1255, 1191, 1170, 1149, 1109, 1038, 1010, 906,865, 822, 797, 743, 663, 562, 465. HR-MS-ESI(+) m / z calcd. for C14H20NO3 [M+H]+ 250.1438, found 250.1440.

Claims

97 CLAIMS 1. Compound of formula (I) or (II)5(I) (II)wherein R1and R2are independently of each other selected from alkyl, cycloalkyl, heterocyclyl, aryl, hetaryl, NRcRd, preferably C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16- membered hetaryl, 5 to 16-membered heterocyclyl, NRcRd, wherein alkyl, cycloalkyl, heterocyclyl,10 aryl, and hetaryl are unsubstituted or substituted; or R1and R2combine to form together with the sulfur atom to which they are attached a 5 to 16- membered hetaryl or heterocyclyl ring that is unsubstituted or substituted; Rsis selected from O and NRa, wherein each Rais independently selected from S(O)mRe, C1-C12- alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered15 heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rc, Rd, and Reare each independently selected from C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16- membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; and 20 m is 1 or 2.

2. The compound according to claim 1, wherein (1) R1and / or R2, preferably both, are selected from unsubstituted or substituted alkyl, cycloalkyl, heterocyclyl, aryl and hetaryl; or 25 (2) R1and R2combine to form together with the sulfur atom to which they are attached a 5 to 16-membered hetaryl or heterocyclyl ring that is monocyclic, bicyclic or tricyclic and is unsubstituted or substituted; or (3) R1and / or R2, preferably both, are selected from tert-butyl, adamantyl, unsubstituted or substituted phenyl, unsubstituted or substituted pyrrolyl, and unsubstituted or substituted30 pyridinyl; or (4) R1and R2combine to form together with the sulfur atom to which they are attached an unsubstituted or substituted ring selected from tetrahydrothiophene, thianthrene, dibenzothiophene, phenothiazine, and tetrahydro-4H,9H-thieno[2,3-d:4,5- d']bis([1,3]dioxine. 35 3. The compound according to claim 1 or 2 selected from the group consisting of:985 wherein Rfis C1-C6-alkyl, C3-C6-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, or 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted. 10 4. Process for producing a compound according to any one of claims 1 to 3, wherein the process comprises reacting a compound of formula (III) or (IV)(III) (IV)wherein each Rpis independently an organic moiety, preferably selected from alkyl, cycloalkyl,15 heterocyclyl, aryl, and hetaryl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, preferably phenyl or alkyl, or wherein two or three Rpcombine to form together with the P atom to which they are attached a 5 to 16-membered hetaryl or heterocyclyl ring that is monocyclic, bicyclic or tricyclic and is unsubstituted or substituted, optionally in presence of a Bronsted base, with nitrous oxide (N2O) to produce the compound according to any one of claims 120 to 3.

5. Process for the production of compounds of formula (V) or (VI)99comprising reacting a compound of formula (I) or (II) with an olefin, preferably a compound of formula (Va) or (VIa) 5 (Va) (VIa)wherein R3, R4, R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12- alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-10 membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R3and R4or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, Rbis selected from C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl,15 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; and wherein Rc, Rd, Re, and m are defined as in claim 1, wherein, preferably, at least one of R3and R4and / or at least one of R5, R6, R7and R8is not hydrogen. 20 6. Process for the production of compounds of formula (VII), (VIII) or (IX)comprising reacting a compound of formula (VI) as defined in claim 5 with an olefin,25 methylenecyclopropane, ketone or aldehyde, preferably a compound of formula (VIIa), (VIIIa) or (IXa) or stereoisomer thereof(VIIa) (VIIIa) (IXa)wherein100 R9a, R9b, R10a, R10b, R11and R12are, independently of each other, selected from H, halogen, CN, C1- C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R9aand R10acombine to form together with the carbon atoms to which they are attached a cyclic 5 group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Reand m are defined as in claim 5; wherein, preferably, in compounds of formula (VIIa) at least one of R9a, R9b, R10aand R10bis not hydrogen and / or one of R9aand R9bin the compounds of formula (IXa) and / or (IX) is hydrogen. 10 7. Process for the production of (1) compounds of formula (X) or (XI)15 comprising subjecting a compound of formula (IX) as defined in claim 6 to conditions that cause the elimination of nitrogen (N2), wherein R5, R6, R7and R8are as defined in claim 5 and R9aand R9bare as defined in claim 6; (2) compounds of formula (XII) 20comprising subjecting a compound of formula (VII) to conditions that cause the elimination of nitrogen (N2), wherein R5, R6, R7and R8are as defined in claim 5 and R9a, R9b, R10aand R10bare as defined in claim 6. 25 8. Process for the production of compounds of formula (XIII) or (XIV)(XIII)comprising reacting a compound of formula (I) or (II) according to any one of claims 1 to 3 with a diene compound, preferably a compound of formula (XIIIa) or stereoisomer thereof101(XIIIa) wherein R13, R14, R15, R16, R17and R18are each independently selected from H, halogen, CN, C1-C12-alkyl, 5 C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, X is selected from C(Rx)2, C=C(Rx)2, C(O), O, S, and NRa; Y is a bond or selected from C(Ry)2, C(O); 10 each Z is selected from C(Rz)2; Rais selected from S(O)mRe, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16- membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rb, Rc, Rd, and Reare each independently selected from H, C1-C12-alkyl, C3-C12-cycloalkyl, C2-C12-15 alkenyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; each Rx, Ryand Rzis independently selected from H, halogen, CN, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and20 hetaryl are unsubstituted or substituted, or one Rxand one Ryand / or one Rxand one Rzand / or two Rzmay combine to form together with the carbon atom to which they are attached a cyclic group selected from 3 to 12-membered cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, 25 one Ryand one Ra, or one Rzand one Ra, or two Ramay combine to form together with the carbon and / or nitrogen atom(s) to which they are attached a cyclic group selected from 5 to 16-membered hetaryl and 5 to 16-membered heterocyclyl, wherein heterocyclyl and hetaryl are unsubstituted or substituted; m is 1 or 2; and 30 n is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1 or 2, more preferably 0 or 1.

9. Process according to any one of claims 5-8, wherein any one of the following compounds is produced102105 5 1010. Use of a compound according to any one of claims 1 to 3 for transfer of a carbon atom or a CN2 group into an organic substrate comprising a pi electron system, preferably an organic substrate comprising a carbon-carbon double bond (C(sp2)-C(sp2) bond), more preferably for introducing a15 single C(sp3) atom into said organic system to create a carbon spiro center.106 11. The process of any one of claims 5 to 9 or the use of claim 10, wherein the compound of any one of claims 1 to 3 is generated in situ.

12. Compounds of formula (XIII) 5wherein R13, R14, R15, R16, R17and R18are each independently selected from H, halogen, CN, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-10 membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, C(O)Re, BRcRd, SnRbRcRd, and SiRbRcRd, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, X is selected from C(Rx)2, C(O), O, S, and NRa; Y is a bond or selected from C(Ry)2 or C(O); 15 Z is selected from C(Rz)2; Rais selected from S(O)mRe, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16- membered hetaryl, and 5 to 16-membered heterocyclyl, wherein alkyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; Rb, Rc, Rd, and Reare each independently selected from H, C1-C12-alkyl, C3-C12-cycloalkyl, C2-C12-20 alkenyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted; each Rx, Ryand Rzis independently selected from H, halogen, CN, C1-C12-alkyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and25 hetaryl are unsubstituted or substituted, or one Rxand one Ryand / or one Rxand one Rzand / or two Rzmay combine to form together with the carbon atom to which they are attached a cyclic group selected from 3 to 12-membered cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, and 5 to 16-membered heterocyclyl, wherein cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, 30 one Ryand one Ra, or one Rzand one Ra, or two Ramay combine to form together with the carbon and / or nitrogen atom(s) to which they are attached a cyclic group selected from 5 to 16-membered hetaryl and 5 to 16-membered heterocyclyl, wherein heterocyclyl and hetaryl are unsubstituted or substituted; m is 1 or 2; and 35 n is 0, 1, 23, 4, 5, or 6, preferably 0, 1 or 2, more preferably 0 or 1, with the proviso that at least one of R13and R14is not hydrogen and wherein compounds where one of R13 and R14 is hydrogen and the other is methyl or ethyl or both of R13 and R14 are methyl areexcluded.107 13. The compound of claim 12, wherein (1) R15and R16are hydrogen; (2) R13and R14are selected from CN, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- 5 membered heterocyclyl, S(O)mRe, ORb, NRcRd, C(O)NRcRd, C(O)ORb, and C(O)Re,wherein aryl and hetaryl are unsubstituted or substituted; (3) one of X and Y is C(O), O, S, or NRa and the other is C(Rx)2 or C(Ry)2;(4) n is 0 or 1; and / or (5) n is 0 and one Rxand one Rycombine to form together with the carbon atoms to which they are10 attached a phenyl ring, which is unsubstituted or substituted.

14. Compound of formula (VI) (VI) wherein 15 R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2- C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, 20 wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Re, and m are defined as in claim 1, wherein, preferably, at least one of R5, R6, R7and R8is not hydrogen.

15. Compound of formula (VII), (VIII), (IX), (X), (XI) or (XII) 2530wherein108 R5, R6, R7and R8are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2- C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16-membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or R5and R7combine to form together with the carbon atoms to which they are attached a cyclic group 5 selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein, preferably, at least one of R5, R6, R7and R8is not hydrogen; R9, R10, R11and R12are, independently of each other, selected from H, halogen, CN, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, 5 to 16-membered aryl, 5 to 16-membered hetaryl, 5 to 16- membered heterocyclyl, S(O)mRe, C(O)NRcRd, C(O)ORb, and C(O)Re, or 10 R9and R10combine to form together with the carbon atoms to which they are attached a cyclic group selected from 3 to 12-membered cycloalkenyl or 5 to 16-membered heterocyclyl, wherein alkyl, alkenyl, cycloalkyl, heterocyclyl, aryl, and hetaryl are unsubstituted or substituted, and wherein Rb, Rc, Rd, Re, and m are defined as in claim 1. 15

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