Method for generating and capturing photocatalytic alkyl free radicals and its products and applications

Abstract

The present application provides a method for photocatalytic generation and capture of alkyl free radicals, and its products and applications of the products, including the following steps: subjecting alkyl neopentylbenzene compounds and capture agents to a photocatalytic reaction under photocatalytic conditions; the general structural formula (I) of the alkyl neopentylbenzene compounds is as follows: the capture agent contains an electron-deficient group. The alkyl neopentylbenzene compounds are induced to break their carbon-carbon bonds by single electron transfer, and then undergo a photocatalytic reaction with the capture agent; the previously unrealized carbon-carbon bond breakage of alkyl neopentylbenzene is achieved, and the reaction substrate range is relatively wide, R1 and R2 can be various types of groups; the generated alkyl free radicals can be captured by a variety of capture agents containing electron-deficient groups, including organic matter containing electron-deficient double bonds or heterocycles, p-toluenesulfonyl cyanide, p-toluenesulfonyl chloride and other capture agents, the reaction process is safe and controllable, and the operation in the preparation and production process is simplified.

Description

Technical Field

[0001] The present application belongs to the technical field of organic compound synthesis, and more specifically, to a method for generating and capturing photocatalytic alkyl free radicals, and its products and applications of the products. Background Art

[0002] With the understanding of photocatalytic mechanism and the development of photoredox catalysts, visible light-induced photoredox catalysis has developed rapidly and achieved remarkable achievements, which has completely changed modern free radical chemistry. Among them, alkyl radicals play an indispensable role in the development of new synthetic methods under photo / electrochemical catalysis.

[0003] Typically, precursors of alkyl radicals undergo single electron transfer with the aid of photocatalysts to generate transient alkyl radicals that can participate in various bond-forming processes in a chemo- and stereo-selective manner. A large number of alkyl radical precursors have been developed, which basically have heteroatomic groups that can be modified. After being modified with functional groups, the energy barrier between the substrate and the excited state of the photosensitizer can be reduced. Despite these advances, little attention has been paid to how to use common, commercially available chemical raw materials with pure alkyl skeletons to generate alkyl radicals in a precisely controlled manner. However, due to the high oxidation potential of pure alkyl skeletons, the direct generation of alkyl radicals from simple unactivated pure alkyl precursors remains an important challenge in photoredox catalysis. Summary of the invention

[0004] Based on this, an object of the present application is to provide a method for photocatalytic generation and capture of alkyl radicals to solve the technical problem existing in the prior art of how to use common, commercially available chemical raw materials with pure alkyl skeletons to produce alkyl radicals in a precisely controlled manner.

[0005] Another object of the present application is to provide a product prepared by the above method.

[0006] Another object of the present application is to provide applications of the above products.

[0007] To achieve the above purpose, the technical solution adopted in this application is:

[0008] A method for photocatalytic generation and capture of alkyl free radicals, comprising the following steps:

[0009] The alkyl neopentylbenzene compound and the capture agent are subjected to a photocatalytic reaction under photocatalytic conditions; the structural formula (I) of the alkyl neopentylbenzene compound is as follows:

[0010]

[0011] R1 and R2 are each independently any one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, arylalkyl, heteroarylalkyl, alkenylalkyl, alkynylalkyl, cyanoalkyl, alkyloxycarbonylalkyl, silylalkyl, halogen, trifluoromethoxy, sulfonamide, heterocyclic aromatic hydrocarbon, ester group, carbonyl group, and hydrogen atom;

[0012] The capture reagent contains an electron-deficient group.

[0013] Optionally, the method of subjecting the alkyl neopentylbenzene compound and the capture agent to a photocatalytic reaction under photocatalytic conditions comprises the following steps:

[0014] Alkyl neopentylbenzene compounds, capture agents, photocatalyst solutions, oxidants and additives are mixed and subjected to photocatalytic reaction under blue light irradiation.

[0015] Optionally, the structure of the capture agent is any of the following:

[0016]

[0017] Corresponding to the capture reagent, the product structure of the photocatalytic reaction is as follows:

[0018]

[0019] R3 is any one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, arylalkyl, heteroarylalkyl, alkenylalkyl, alkynylalkyl, cyanoalkyl, alkyloxycarbonylalkyl, silylalkyl, halogen, trifluoromethoxy, sulfonamide, heterocyclic aromatic hydrocarbon, ester group, carbonyl group and hydrogen atom.

[0020] Optionally, the photocatalyst is an acridinium salt catalyst.

[0021] Optionally, the general structural formula of the acridinium salt catalyst is as follows:

[0022]

[0023] Wherein, X is a tetrafluoroborate anion, a hexafluorophosphate anion or a perchlorate anion; Ar is an aryl group or a substituted aryl group; R7 is any one of an alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a heteroalkenyl group, a cycloalkenyl group, a heterocycloalkenyl group, an alkynyl group, a heteroalkynyl group, a cycloalkynyl group, a heterocycloalkynyl group, an alkoxy group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, an aryloxy group, a heteroaryloxy group, an arylalkyl group, a heteroarylalkyl group, an alkenylalkyl group, an alkynylalkyl group, and a cyanoalkyl group.

[0024] Optionally, the oxidant comprises at least one of persulfate, high-valent iodine compounds, quinones, potassium permanganate, peroxide, oxygen and N-fluorobenzenesulfonimide;

[0025] And / or, the additive is water.

[0026] Optionally, the molar ratio of the photocatalyst, the oxidant and the additive is (0.1-20):(0.1-20):(0.2-40).

[0027] Optionally, the general structural formula (I) includes any one of the following structural formulas:

[0028]

[0029]

[0030] And, a product prepared by the above-mentioned method of photocatalytic alkyl radical generation and capture.

[0031] And, the application of the above products in the synthesis of drug intermediates, functional materials and metal ligand preparation.

[0032] The beneficial effects provided by this application are:

[0033] 1. The method of photocatalytic alkyl radical generation and capture is to transfer a single electron to an alkyl neopentylbenzene compound, thereby inducing the carbon-carbon bond to break, and then photocatalytically react with the capture reagent, which has the following advantages:

[0034] First, the previously unrealized carbon-carbon bond cleavage of alkyl neopentylbenzene was achieved, and the reaction substrate range is relatively wide, R1 and R2 can be various types of groups;

[0035] Second, the generated alkyl radicals can be captured by a variety of capture reagents containing electron-deficient groups, including organic substances containing electron-deficient double bonds or heterocyclic rings, p-toluenesulfonyl cyanide, p-toluenesulfonyl chloride and other capture reagents. The reaction process is safe and controllable, simplifying the operation in the preparation and production process;

[0036] Third, the production cost of preparing such capture products is significantly reduced, and the designability and application prospects of such compounds are greatly expanded;

[0037] 2. The addition product obtained by the method of the present application has high functionality, making it more diversified in the application of drug intermediate synthesis, functional materials and metal ligands. It can be widely used in the synthesis of drug intermediates, the preparation of chiral ligands and functional materials, and can effectively reduce the economic cost of the preparation of drug intermediates and functional materials, and is environmentally friendly. DETAILED DESCRIPTION

[0038] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail in the following embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0039] The compounds and their derivatives involved in the embodiments of the present invention are named according to the IUPAC (International Union of Pure and Applied Chemistry) or CAS (Chemical Abstracts Service, Columbus, Ohio) naming system. Therefore, the compound groups specifically involved in the embodiments of the present invention are described and explained as follows:

[0040] With respect to "hydrocarbon groups", the minimum and maximum carbon atom content of the hydrocarbon group is indicated by a prefix, for example, the prefix (C-C) alkyl represents any alkyl group containing from "a" to "b" carbon atoms. Thus, for example, (C1-C6) alkyl refers to an alkyl group containing from one to six carbon atoms.

[0041] "Alkoxy" refers to a straight or branched, monovalent, saturated aliphatic chain bonded to an oxygen atom, including but not limited to methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy and other similar groups. (Ca-Cb) alkoxy refers to any straight or branched, monovalent, saturated aliphatic chain bonded to an oxygen atom in an alkyl group containing "a" to "b" carbon atoms.

[0042] "Alkyl" refers to a linear or branched, monovalent, saturated fatty chain, including but not limited to methyl, ethyl and other similar groups. "Heteroalkyl" refers to a linear or branched, monovalent, saturated fatty chain attached to at least one heteroatom, such as methylaminoethyl or other similar groups.

[0043] "Alkenyl" refers to a straight or branched hydrocarbon with at least one double bond, including but not limited to vinyl, propenyl and other similar groups. "Heteroalkenyl" refers to a straight or branched hydrocarbon with one or more double bonds connected to at least one heteroatom, including but not limited to vinylaminoethyl or other similar groups.

[0044] "Alkynyl" refers to a straight or branched hydrocarbon with at least one triple bond, including but not limited to ethynyl, propynyl, and other similar groups. "Heteroalkynyl" refers to a straight or branched hydrocarbon with one or more triple bonds attached to at least one heteroatom, including but not limited to ethynyl, propynyl, and other similar groups.

[0045] "Aryl" refers to a cyclic aromatic hydrocarbon, including but not limited to phenyl, naphthyl, anthracenyl, phenanthrenyl and other similar groups. "Heteroaryl" refers to a monocyclic or polycyclic or condensed ring aromatic hydrocarbon, in which at least one or carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heteroaryl contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl includes but is not limited to benzofuranyl, benzothiophenyl, benzimidazolyl, benzoxazolyl, benzothiazolyl and other similar groups.

[0046] "Cycloalkyl" refers to a saturated monocyclic or polycyclic alkyl group, which may be fused to an aromatic hydrocarbon group. Cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indanyl, tetrahydronaphthyl, and other similar groups. "Heterocycloalkyl" refers to a saturated monocyclic or polycyclic alkyl group, which may be fused to an aromatic hydrocarbon group, wherein at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen, or sulfur. If the heterocycloalkyl contains more than one heteroatom, these heteroatoms may be the same or different. Heterocycloalkyl includes, but is not limited to, azepanyl, azetidinyl, dihydroindole, morpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, tetrahydrofuranyl, and other similar groups.

[0047] "Cycloalkenyl" refers to a monocyclic or polycyclic alkenyl group with at least one double bond, which may be fused to an aromatic hydrocarbon group, including but not limited to cyclovinyl, cyclopropenyl or other similar groups. "Heterocycloalkenyl" refers to a monocyclic or polycyclic alkenyl group with at least one double bond, which may be fused to an aromatic hydrocarbon group, wherein at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains multiple heteroatoms, these heteroatoms may be the same or different.

[0048] "Cycloalkynyl" refers to a monocyclic or polycyclic alkynyl group with at least one triple bond, which may be fused to an aromatic hydrocarbon group, including but not limited to cycloethynyl, cyclopropynyl or other similar groups. "Heterocycloalkynyl" refers to a monocyclic or polycyclic alkynyl group with at least one triple bond, which may be fused to an aromatic hydrocarbon group, wherein at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains multiple heteroatoms, these heteroatoms may be the same or different.

[0049] A method for generating and capturing photocatalytic alkyl radicals in an embodiment of the present application comprises the following steps:

[0050] The alkyl neopentylbenzene compound and the capture agent are subjected to a photocatalytic reaction under photocatalytic conditions; the structural formula (I) of the alkyl neopentylbenzene compound is as follows:

[0051]

[0052] R1 and R2 are each independently any one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, arylalkyl, heteroarylalkyl, alkenylalkyl, alkynylalkyl, cyanoalkyl, alkyloxycarbonylalkyl, silylalkyl, halogen, trifluoromethoxy, sulfonamide, heterocyclic aromatic hydrocarbon, ester group, carbonyl group and hydrogen atom.

[0053] The capture reagent contains an electron-deficient group.

[0054] The method for photocatalytic alkyl radical generation and capture in the embodiment of the present application transfers a single electron to an alkyl neopentylbenzene compound, thereby inducing the cleavage of the carbon-carbon bond, and then photocatalytically reacts with a capture agent. The reactant alkyl neopentylbenzene compound acts as a nucleophilic agent, which can attack substrates such as electron-deficient olefins and heterocycles, i.e., the capture agent, so that the alkyl neopentylbenzene compound and the capture agent undergo an addition reaction, which not only effectively improves the atomic utilization of the reactants, but also broadens the limitations of the substrate, thereby efficiently and greenly preparing a target product precursor with high enantioselectivity and a wide range, and then obtaining a product with potential application value through a simple reduction reaction.

[0055] Alternatively, R1 and R2 are each independently C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C2-C20 alkenyl, C2-C20 heteroalkenyl, C3-C20 cycloalkenyl, C3-C20 heterocycloalkenyl, C2-C20 alkynyl, C2-C20 heteroalkynyl, C3-C20 cycloalkynyl, C3-C20 heterocycloalkynyl, C1-C20 alkoxy, aryl, Any one of substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C1-C20) alkyl, heteroaryl (C1-C20) alkyl, C2-C20 alkenyl (C1-C20) alkyl, C2-C20 alkynyl (C1-C20) alkyl, cyano (C1-C20) alkyl, alkyloxycarbonyl alkyl, silyl alkyl C3-C20, halogen, trifluoromethoxy, sulfonamide, hydrogen atom. Among them, heterocycles include quinoline, pyridine, thiazole, benzothiazole, pyrazine, pyrimidine, purine and other nitrogen-containing and sulfur-containing heterocycles.

[0056] Optionally, the method of subjecting the alkyl neopentylbenzene compound and the capture agent to a photocatalytic reaction under photocatalytic conditions comprises the following steps:

[0057] Alkyl neopentylbenzene compounds, capture agents, photocatalyst solutions, oxidants and additives are mixed and subjected to photocatalytic reaction under blue light irradiation.

[0058] Optionally, the structure of the capture agent is any of the following:

[0059]

[0060] Corresponding to the capture reagent, the product structure of the photocatalytic reaction is as follows:

[0061]

[0062] R3 is any one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, heterocycloalkynyl, alkoxy, alkyloxycarbonylalkyl, arylalkyl, alkenylalkyl, alkynylalkyl, cyanoalkylaryl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, silylalkyl, halogen, heterocyclic aromatic hydrocarbon, ester group, alkoxy group, carbonyl group and hydrogen atom.

[0063] R1, R2 and R3 may be the same or different.

[0064] The C1-C20 alkyl group may be (C1-C10) alkyl, (C1-C5) alkyl, (C1-C4) alkyl, (C1-C3) alkyl, (C1-C2) alkyl, etc., for example, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, etc.

[0065] The (C1-C20)heteroalkyl group may be a (C1-C10)heteroalkyl group, a (C1-C5)heteroalkyl group, a (C1-C4)heteroalkyl group, a (C1-C3)heteroalkyl group, a (C1-C2)heteroalkyl group, and the heteroatoms may be halogen, nitrogen atom, sulfur atom, etc.

[0066] The (C3-C20)cycloalkyl group may be a (C3-C10)cycloalkyl group, a (C3-C5)cycloalkyl group, a (C3-C4)cycloalkyl group, and the like, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and the like.

[0067] The (C3-C20)heterocycloalkyl group may be a (C3-C10)heterocycloalkyl group, a (C3-C10)heterocycloalkyl group, a (C3-C5)heterocycloalkyl group, a (C3-C4)heterocycloalkyl group, etc., and the heteroatom may be a halogen, a nitrogen atom, a sulfur atom, etc.

[0068] The (C2-C20)alkenyl group may be a (C3-C10)alkenyl group, a (C3-C5)alkenyl group, a (C3-C4)alkenyl group, a (C2-C3)alkenyl group, and the like, for example, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like.

[0069] The (C2-C20)heteroalkenyl group may be a (C2-C10)heteroalkenyl group, a (C3-C10)heteroalkenyl group, a (C3-C5)heteroalkenyl group, a (C3-C4)heteroalkenyl group, a (C2-C3)heteroalkenyl group, and the like, wherein heteroatoms are, for example, halogens, nitrogen atoms, sulfur atoms, and the like.

[0070] The (C3-C20)cycloalkenyl group may be a (C3-C10)cycloalkenyl group, a (C3-C5)cycloalkenyl group, a (C3-C4)cycloalkenyl group, and the like, for example, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and the like.

[0071] The (C3-C20)heterocycloalkenyl group may be a (C3-C10)heterocycloalkenyl group, a (C3-C5)heterocycloalkenyl group, a (C3-C4)heterocycloalkenyl group, etc., wherein the hetero atom may be a halogen, a nitrogen atom, a sulfur atom, etc.

[0072] The (C2-C20)alkynyl group may be a (C2-C10)alkynyl group, a (C3-C10)alkynyl group, a (C3-C5)alkynyl group, a (C3-C4)alkynyl group, a (C2-C3)alkynyl group, for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, and the like.

[0073] The (C2-C20)heteroalkynyl group may be a (C2-C10)heteroalkynyl group, a (C3-C10)heteroalkynyl group, a (C3-C5)heteroalkynyl group, a (C3-C4)heteroalkynyl group, a (C2-C3)heteroalkynyl group, and the like, wherein a heteroatom is, for example, a halogen, a nitrogen atom, a sulfur atom, and the like.

[0074] The (C3-C20)cycloalkynyl group may be a (C3-C10)cycloalkynyl group, a (C3-C5)cycloalkynyl group, a (C3-C4)cycloalkynyl group, etc., and the (C2-C20)cycloalkynyl group may be a cyclopropynyl group, a cyclobutynyl group, a cyclopentynyl group, etc.

[0075] The (C3-C20)heterocycloalkynyl group may be a (C3-C10)heterocycloalkynyl group, a (C3-C5)heterocycloalkynyl group, a (C3-C4)heterocycloalkynyl group, etc., and the heteroatom in the (C3-C20)heterocycloalkynyl group may be a halogen, a nitrogen atom, a sulfur atom, etc.

[0076] The (C1-C20)alkoxy group can be a (C1-C10)alkoxy group, a (C1-C8)alkoxy group, a (C1-C6)alkoxy group, a (C1-C4)alkoxy group, a (C1-C3)alkoxy group, a (C1-C2)alkoxy group, and the (C1-C20)alkoxy group can be, but is not limited to, a methyloxy group, an ethyloxy group, a propyloxy group, and the like.

[0077] The aryl group may be, but is not limited to, a monocyclic aryl group, a polycyclic aryl group, or a condensed-ring aryl group.

[0078] The substituted aryl group may be, but is not limited to, a single or multiple substituted phenyl group at the ortho, meta, or para positions. The substituents include, but are not limited to, alkyl, substituted alkyl, halogen, alkoxyamino, nitro, -NR5R6, -NR5-CO-NR6, -OCONR5, -PR5R6, -SOR5, -SO2-R5, -SiR5R6R7, -BR5R6, etc. R5, R6, and R7 may be groups as shown in R1 and R2 above, wherein when the substituent is an alkyl group, the alkyl group may be, for example, but not limited to, methyl, ethyl, propyl, butyl, and isobutyl. When the substituent is a substituted alkyl group, the substituted alkyl group may be, for example, but not limited to, trifluoromethyl, trichloromethyl, trifluoroethyl, and trichloroethyl; when the substituent is a halogen, the halogen may be, for example, but not limited to, fluorine, chlorine, bromine, and iodine; when the substituent is an alkoxy group, the alkoxy group may be, for example, but not limited to, methyloxy, ethyloxy, and propyloxy. The substituted aryl group may also be cyano(C1-C10)alkyl(C3-C8)aryl, or substituted (C3-C8)aryl.

[0079] The heteroaryl group may be (C3-C8) heteroaryl, furan, thiophene.

[0080] The substituted heteroaryl group may be a substituted (C3-C8) heteroaryl group, an alkoxy-substituted furan group, a (C3-C8) heteroaryl-substituted furan group, or an aliphatic chain-substituted thiophene group.

[0081] Aryloxy may be phenoxy, naphthyloxy, anthracenyloxy or phenanthrenyloxy.

[0082] Aryl (C1-C20) alkyl can be aryl (C1-C10) alkyl, phenyl (C1-C10) alkyl, phenyl (C1-C5) alkyl, phenyl (C1-C4) alkyl, phenyl (C1-C3) alkyl, phenyl (C1-C2) alkyl, etc. In some embodiments, aryl (C1-C20) alkyl can be phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylisobutyl, phenylpentyl, phenylisopentyl, phenylneopentyl.

[0083] Heteroaryl (C1-C20) alkyl can be heteroaryl (C1-C10) alkyl, heteroaryl (C1-C10) alkyl, heteroaryl (C1-C5) alkyl, heteroaryl (C1-C4) alkyl, heteroaryl (C1-C3) alkyl, heteroaryl (C1-C2) alkyl, etc. Among them, the heteroaryl can be (C3-C8) heteroaryl, furan, pyridine, etc.

[0084] (C2-C20)alkenyl(C1-C20)alkyl can be (C2-C10)alkenyl(C1-C10), (C2-C5)alkenyl(C1-C3), for example 2-butenyl, 2-pentenyl, 3-hexenyl, 3-heptenyl and the like.

[0085] (C2-C20)alkynyl(C1-C20)alkyl can be (C2-C10)alkynyl(C1-C10)alkyl, (C2-C5)alkynyl(C1-C3)alkyl, for example 2-butynyl, 2-pentynyl, 3-hexynyl, 3-heptynyl and the like.

[0086] The cyano (C1-C20) alkyl group may be a cyano (C1-C10) alkyl group, a cyano (C1-C5) alkyl group, a cyano (C1-C4) alkyl group, a cyano (C1-C3) alkyl group, a cyano (C1-C2) alkyl group, etc. In some embodiments, the cyano (C1-C20) alkyl group may be a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, a cyanopentyl group, etc.

[0087] The alkyloxycarbonylalkyl group may be (C1-C10)alkyloxycarbonyl(C1-C10)alkyl, (C1-C5)alkyloxycarbonyl(C1-C5)alkyl, (C1-C4)alkyloxycarbonyl(C1-C4)alkyl, (C1-C3)alkyloxycarbonyl(C1-C3)alkyl, (C1-C2)alkyloxycarbonyl(C1-C2)alkyl, etc. In some embodiments, the alkyloxycarbonylalkyl group may be ethoxycarbonylethyl, ethoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylmethyl, propoxycarbonylpropyl, propoxycarbonylethyl, propoxycarbonylmethyl, etc.

[0088] The photocatalytic reaction formulas of the alkyl neopentylbenzene compounds and the above-mentioned capture agents are as follows:

[0089]

[0090]

[0091] Optionally, the photocatalyst is an acridinium salt catalyst.

[0092] Optionally, the general structural formula of the acridinium salt catalyst is as follows:

[0093]

[0094] Wherein, X is a tetrafluoroborate anion, a hexafluorophosphate anion or a perchlorate anion; Ar is an aryl group or a substituted aryl group; R7 is any one of an alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a heteroalkenyl group, a cycloalkenyl group, a heterocycloalkenyl group, an alkynyl group, a heteroalkynyl group, a cycloalkynyl group, a heterocycloalkynyl group, an alkoxy group, an aryl group, a substituted aryl group, a heteroaryl group, a substituted heteroaryl group, an aryloxy group, a heteroaryloxy group, an arylalkyl group, a heteroarylalkyl group, an alkenylalkyl group, an alkynylalkyl group, and a cyanoalkyl group.

[0095] Optionally, the oxidant includes at least one of persulfate, high-valent iodine compounds, quinones, potassium permanganate, peroxide, oxygen and N-fluorobenzenesulfonimide.

[0096] Optionally, the additive is water.

[0097] The synergistic effect of acridinium salt catalysts, oxidants, and additive water, on the one hand, reduces the toxicity of the photocatalytic system of the embodiment of the present application, improves the atomic utilization rate and reaction efficiency, and produces fewer by-products; on the other hand, it makes the photocatalytic reaction process safe and controllable, and simplifies the operation in the preparation and production process. Among them, acridinium salt catalysts can provide better single-electron oxidation, thereby improving the efficiency of carbon-carbon bond breaking during the catalytic reaction.

[0098] Optionally, the molar ratio of the photocatalyst, the oxidant and the additive water is (0.1-20): (0.1-20): (0.2-40). Within this molar ratio range, under the synergistic effect of the photocatalyst, the oxidant and the water, the photocatalytic reaction has a high catalytic efficiency, which is beneficial to improve the yield of the reaction product. Preferably, the molar ratio of the photocatalyst, the oxidant and the water is (0.2-20): 2.5: (1-10), which is beneficial to obtain the target product with the highest yield.

[0099] Optionally, the general structural formula (I) includes any one of the following structural formulas:

[0100]

[0101] The method for photocatalytic generation and capture of alkyl radicals in the embodiment of the present application has the following advantages:

[0102] First, the previously unrealized carbon-carbon bond cleavage of alkyl neopentylbenzene was achieved, and the reaction substrate range is relatively wide, R1 and R2 can be various types of groups;

[0103] Second, the generated alkyl radicals can be captured by a variety of capture reagents containing electron-deficient groups, including organic substances containing electron-deficient double bonds or heterocyclic rings, p-toluenesulfonyl cyanide, p-toluenesulfonyl chloride and other capture reagents. The reaction process is safe and controllable, which simplifies the operation in the preparation and production process. It is worth noting that the widely used core lactones and epiandrosterone can be well modified, and the production process is simple, controllable and efficient.

[0104] Third, the reactant raw materials are very easy to obtain, and the reactants do not need additional modification before the reaction and can be directly used for preparation and production, which simplifies the operation steps, shortens the reaction route, significantly reduces the production cost of preparing such capture products, and greatly expands the designability and application prospects of such compounds.

[0105] The addition product obtained by the method of the embodiment of the present application has high functionality, making it more diversified in the application of drug intermediate synthesis, functional materials and metal ligands. It can be used as a precursor of the target product and is widely used in the synthesis of drug intermediates, the preparation of chiral ligands and functional materials. It can effectively reduce the economic cost of the preparation of drug intermediates and functional materials and is environmentally friendly.

[0106] The following is illustrated by multiple embodiments.

[0107] Example 1

[0108] This embodiment provides a compound 2-(1,2-diphenylpropyl)malononitrile and a preparation method thereof. The structural formula of 2-(1,2-diphenylpropyl)malononitrile is shown in the following molecular structural formula 1:

[0109]

[0110] The preparation method of 2-(1,2-diphenylpropyl)malononitrile of the present embodiment comprises the following steps:

[0111] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent benzalmalononitrile (0.2 mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, and nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0112] The structure of alkyl neopentylbenzene is as follows:

[0113]

[0114] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0115] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 78%.

[0116] Related characterization analysis, the result is enantiomer 1: 1H NMR(500MHz,Chloroform-d)δ7.57–7.52(m,2H),7.52–7.42(m,5H),7.41–7.33(m,3H),3.62(d, J=4.1Hz,1H),3.42(dq,J=11.5,6.8Hz,1H),3.22(dd,J=11.7,4.1Hz,1H),1.16(d,J=6.8Hz,3H). 13 C NMR (126 MHz, Chloroform-d) δ 142.44, 135.58, 129.72, 129.34, 129.18, 128.59, 128.13, 127.14, 112.18, 111.48, 53.63, 42.09, 28.75, 20.64. Enantiomer 2: 1 H NMR(500MHz,Chloroform-d)δ7.32–7.24(m,3H),7.24–7.15(m,3H),7.05–6.99(m,2H),6.99–6.94 (m,2H),4.11(d,J=7.6Hz,1H),3.52(q,J=7.2Hz,1H),3.44(t,J=7.8Hz,1H),1.46(d,J=6.9Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ140.72,134.95,128.79,128.67,128.60,128.48,128. 09,127.32,112.46,111.95,52.59,41.65,27.60,20.13.HRMS(ESI-TOF)calculated forC 18 H 16 N2(MH + ):259.1241,found:259.1241. This result further confirmed that the molecular structure of the product was just as the above molecular structure 1.

[0117] Example 2

[0118] This embodiment provides a compound 2-(2-(4-(tert-butyl)phenyl)-1-phenylpropyl)malononitrile and a preparation method thereof. The structural formula of 2-(2-(4-(tert-butyl)phenyl)-1-phenylpropyl)malononitrile is shown in the following molecular structural formula 2:

[0119]

[0120] The preparation method of 2-(2-(4-(tert-butyl)phenyl)-1-phenylpropyl)malononitrile of the present embodiment comprises the following steps:

[0121] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent benzalmalononitrile (0.2 mmol, 30.8 mg) and the oxidant sodium persulfate (0.5 mmol, 119 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, and nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0122] The structure of alkyl neopentylbenzene is as follows:

[0123]

[0124] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0125] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 65%.

[0126] Related characterization analysis, the result is enantiomer 1: 1 H NMR(400MHz,Chloroform-d)δ7.59–7.43(m,7H),7.36–7.30(m,2H),3.67(d,J=4.1Hz,1H),3. 41(dq,J=11.6,6.8Hz,1H),3.21(dd,J=11.7,4.1Hz,1H),1.38(s,9H),1.16(d,J=6.8Hz,3H). 13 C NMR (101 MHz, Chloroform-d) δ 151.08, 139.23, 135.66, 129.26, 129.07, 128.59, 126.71, 126.55, 112.30, 111.56, 53.72, 41.51, 34.61, 31.34, 28.80, 20.57. Enantiomer 2: 1 H NMR(400MHz,Chloroform-d)δ7.35–7.28(m,3H),7.28–7.22(m,2H),7.02–6.95(m,2H),6.93 –6.87(m,2H),4.07(d,J=8.3Hz,1H),3.59–3.41(m,2H),1.42(d,J=6.8Hz,3H),1.30(s,9H). 13C NMR(101MHz,Chloroform-d)δ150.33,137.00,134.69,128.91,128.58,128.4 5,127.90,125.27,112.63,112.03,52.58,40.93,34.44,31.29,27.47,19.93. HRMS(ESI-TOF)calculated for C 22 H 24 N2(MH + ):315.1867,found:315.1867. This result further confirmed that the molecular structure of the product was just as the above molecular structure 2.

[0127] Example 3

[0128] This embodiment provides a compound 2-(1,2-diphenylhexyl)malononitrile and a preparation method thereof. The structural formula of 2-(1,2-diphenylhexyl)malononitrile is shown in the following molecular structural formula 3:

[0129]

[0130] The preparation method of 2-(1,2-diphenylhexyl)malononitrile of the present embodiment comprises the following steps:

[0131] S01: The photocatalyst Mes-Acr-MeBF4 (0.01 mmol, 4.0 mg), the capture reagent benzalmalononitrile (0.2 mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, and nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0132] The structure of alkyl neopentylbenzene is as follows:

[0133]

[0134] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0135] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 69%.

[0136] Related characterization analysis, the result is a mixture of enantiomers: 1H NMR(500MHz,Chloroform-d)δ7.60–7.40(m,8H),7.39–7.17(m,9H),6.96–6.88(m,3H),4.05(d,J=8.7Hz,1H),3.60–3.50(m,2H),3.32(ddd,J=11 .3,7.1,4.7Hz,1H),3.29–3.19(m,2H),1.85–1.60(m,2H),1.52–1.39(m, 2H),1.38–1.04(m,6H),1.03–0.90(m,2H),0.77(dt,J=75.0,7.2Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ140.56,138.34,135.75,134.70,129.65,129.33,129.12,128.99,128.87,128.59,128.46,128.37,128.0,127.38,112 .62,112.20,111.98,111.47,52.82,51.58,47.61,47.30,33.54,33.21,29.46,28.84,27.39,22.52,22.18,13.92,13.78.HRMS(ESI-TOF)calculated for C 21 H 22 N2(MH + ):301.1710, found:301.1711. This result further confirmed that the molecular structure of the product was just as the above molecular structure 3.

[0137] Example 4

[0138] This embodiment provides a compound 2-(1,2-diphenyltetradecyl)malononitrile and a preparation method thereof. The structural formula of 2-(1,2-diphenyltetradecyl)malononitrile is shown in the following molecular structural formula 4:

[0139]

[0140] The preparation method of 2-(1,2-diphenyltetradecyl)malononitrile of the present embodiment comprises the following steps:

[0141] S01: The photocatalyst Mes-Acr-MeBF4 (0.01 mmol, 4.0 mg), the capture reagent benzalmalononitrile (0.2 mmol, 30.8 mg) and the oxidant potassium persulfate (0.5 mmol, 135 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0142] The structure of alkyl neopentylbenzene is as follows:

[0143]

[0144] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0145] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 69%.

[0146] Related characterization analysis, the result is a mixture of enantiomers: 1 H NMR(500MHz,Chloroform-d)δ7.56–7.29(m,11H),7.29–7.16(m,6H),6.95–6.86(m,3H),4.04(d,J=8.7Hz,1H),3.61–3.45(m,2 H),3.32(ddd,J=11.3,7.0,4.6Hz,1H),3.28–3.18(m,2H),1.83–1.61(m,2H),1.36–0.93(m,42H),0.89(td,J=7.0,3.4Hz,6H). 13CNMR(126MHz,Chloroform-d)δ140.60,138.37,135.78,134.73,129.67,129.35,129.14,129.0 2,128.91,128.61,128.56,128.48,128.38,128.10,127.86,127.41,112.64,112.22,111.99,1 11.49,52.87,51.62,47.65,47.35,33.83,33.54,31.95,29.67,29.63,29.56,29.46,29.43,29 .39,29.36,29.29,29.10,28.85,27.41,27.32,27.28,22.73,14.17.HRMS(ESI-TOF)calculated for C 29 H 38 N2(MH + ):413.2962,found:413.2964. This result further confirmed that the molecular structure of the product was just as the above molecular structure 4.

[0147] Example 5

[0148] This embodiment provides a compound (3-phenylbutane-1,1-methylsulfonyl)benzene and a preparation method thereof. The structural formula of (3-phenylbutane-1,1-methylsulfonyl)benzene is shown in the following molecular structural formula 5:

[0149]

[0150] The preparation method of (3-phenylbutane-1,1-methylsulfonyl)benzene of the present embodiment comprises the following steps:

[0151] S01: The photocatalyst Mes-Acr-MeBF4 (0.01 mmol, 4.0 mg), the capture agent (0.2 mmol) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0152] The structure of the capture reagent is as follows:

[0153]

[0154] The structure of alkyl neopentylbenzene is as follows:

[0155]

[0156] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0157] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 79%.

[0158] The results of the relevant characterization analysis are as follows: 1 H NMR(400MHz,Chloroform-d)δ8.04–7.91(m,2H),7.76–7.56(m,6H),7.53–7.44(m,2H),7.28–7.18 (m,3H),4.26–4.13(m,1H),3.25(dt,J=8.9,6.8Hz,1H),2.49–2.30(m,2H),1.27(d,J=7.0Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ143.31,138.20,137.69,134.59,134.31,129.62,129.23,129. 12,129.07,128.89,127.29,126.90,81.17,37.78,33.39,22.64.HRMS(ESI-TOF)calculated for C 22 H 22 O4S2(MH + ):413.0887,found:413.0887. This result further confirmed that the molecular structure of the product was just as the above molecular structure 5.

[0159] Example 6

[0160] This embodiment provides a compound (3-(3-fluorophenyl)butane-1,1-diyldisulfonyl)biphenyl and a preparation method thereof. The structural formula of (3-(3-fluorophenyl)butane-1,1-diyldisulfonyl)biphenyl is as follows:

[0161] As shown in formula 6:

[0162]

[0163] The preparation method of (3-(3-fluorophenyl)butane-1,1-diyldisulfonyl)diphenyl of the present embodiment comprises the following steps:

[0164] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture agent (0.2 mmol) and the oxidant sodium persulfate (0.5 mmol, 119 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0165] The structure of the capture reagent is as follows:

[0166]

[0167] The structure of alkyl neopentylbenzene is as follows:

[0168]

[0169] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0170] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 55%.

[0171] The results of the relevant characterization analysis are 1 H NMR(400MHz,Chloroform-d)δ8.06–7.94(m,2H),7.78–7.66(m,4H),7.62(dd,J=8.5 ,7.3Hz,2H),7.55–7.48(m,2H),7.23(td,J=8.0,6.0Hz,1H),6.91(tdd,J=8.4,2.6,1 .0Hz,1H),6.86(dt,J=7.6,1.2Hz,1H),6.60(dt,J=9.9,2.1Hz,1H),4.16(dd,J=9.2 ,2.5Hz,1H),3.29(tq,J=11.8,6.7Hz,1H),2.51–2.26(m,2H),1.25(d,J=7.0Hz,3H). 13C NMR(101MHz,Chloroform-d)δ162.98(d,J=247.2Hz),146.04(d,J=6.7Hz),138.12,137.39,134.69,134.54,130.33(d,J=8.3Hz ),129.64,129.18,129.15,129.12,123.19(d,J=2.7Hz),113.99(d,J=8.6Hz),113.79(d,J=8.6Hz),81.05,37.60,33.47,22.39. 19 F NMR(376MHz,Chloroform-d)δ-111.75.HRMS(ESI-TOF)calculated for C 22 H 21 FO4S2(MH + ):431.0793,found:431.0793. This result further confirmed that the molecular structure of the product was just as the above molecular structure 6.

[0172] Example 7

[0173] This embodiment provides a compound (3-(4-chlorophenyl)butane-1,1-diyldisulfonyl)biphenyl and a preparation method thereof. The structural formula of (3-(4-chlorophenyl)butane-1,1-diyldisulfonyl)biphenyl is as follows:

[0174] As shown in formula 7:

[0175]

[0176] The preparation method of (3-(4-chlorophenyl)butane-1,1-diyldisulfonyl)diphenyl of the present embodiment comprises the following steps:

[0177] S01: The photocatalyst Mes-Acr-MeBF4 (0.01 mmol, 4.0 mg), the capture agent (0.2 mmol) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0178] The structure of the capture reagent is as follows:

[0179]

[0180] The structure of alkyl neopentylbenzene is as follows:

[0181]

[0182] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0183] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 67%.

[0184] The results of the relevant characterization analysis are 1 H NMR(500MHz,Chloroform-d)δ8.00–7.91(m,2H),7.75–7.62(m,4H),7.60(t,J=7.9Hz,2H),7.53–7.46(m,2H),7.21–7.13(m, 2H),6.98–6.87(m,2H),4.12(dd,J=9.0,2.6Hz,1H),3.24(tt,J=11.8,6.9Hz,1H),2.47–2.28(m,2H),1.23(d,J=6.9Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ141.88,138.06,137.61,134.73,134.46,132.64,129.97,129. 66,129.22,129.16,129.03,128.63,81.12,37.35,33.44,22.57.HRMS(ESI-TOF)calculated for C 22 H 21 ClO4S2(MH + ):447.0497,found:447.0499. This result further confirmed that the molecular structure of the product was just as the above molecular structure 7.

[0185] Example 8

[0186] This embodiment provides a compound (3-(4-(trifluoromethoxy)phenyl)butane-1,1-diyldisulfonyl)biphenyl and a preparation method thereof. The structural formula of (3-(4-(trifluoromethoxy)phenyl)butane-1,1-diyldisulfonyl)biphenyl is shown in the following molecular structural formula 8:

[0187]

[0188] The preparation method of (3-(4-chlorophenyl)butane-1,1-diyldisulfonyl)diphenyl of the present embodiment comprises the following steps:

[0189] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent (0.2 mmol) and the oxidant potassium persulfate (0.5 mmol, 135 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0190] The structure of the capture reagent is as follows:

[0191]

[0192] The structure of alkyl neopentylbenzene is as follows:

[0193]

[0194] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0195] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 67%.

[0196] The results of the relevant characterization analysis are 1 H NMR(400MHz,Chloroform-d)δ8.03–7.92(m,2H),7.78–7.58(m,6H),7.54–7.45(m,2H),7.08(q,J=8 .7Hz,4H),4.14–4.07(m,1H),3.31(dp,J=9.9,6.8Hz,1H),2.49–2.34(m,2H),1.27(d,J=6.9Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ147.96,142.15,137.88,137.66,134.72,134.42,129.68,12 9.16,129.13,129.11,128.64,121.35,120.46(q,J=256.9Hz),81.13,37.27,33.36,22.57. 19 F NMR(376MHz,Chloroform-d)δ-57.83.HRMS(ESI-TOF)calculated for C 23 H 21 F3O5S2(MH +):497.0710, found:497.0713. This result further confirmed that the molecular structure of the product was just as the above molecular structure 8.

[0197] Example 9

[0198] This embodiment provides a compound (3-phenylpentane-1,1-methylsulfonyl)benzene and a preparation method thereof. The structural formula of (3-phenylpentane-1,1-methylsulfonyl)benzene is shown in the following molecular structural formula 9:

[0199]

[0200] The preparation method of (3-phenylpentane-1,1-methylsulfonyl)benzene of the present embodiment comprises the following steps:

[0201] S01: The photocatalyst Mes-Acr-MeBF4 (0.01 mmol, 4.0 mg), the capture agent (0.2 mmol) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0202] The structure of the capture reagent is as follows:

[0203]

[0204] The structure of alkyl neopentylbenzene is as follows:

[0205]

[0206] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0207] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 63%.

[0208] The results of the relevant characterization analysis are 1H NMR(400MHz,Chloroform-d)δ8.02–7.92(m,2H),7.77–7.70(m,1H),7.70–7.57(m,5H),7.52–7.42(m,2H),7.24(dd,J=4.9,1.9Hz,3H),7.02–6.92 (m,2H),4.17(dd,J=9.4,2.2Hz,1H),2.97(dp,J=14.2,5.1Hz,1H),2.55– 2.36(m,2H),1.73–1.60(m,1H),1.60–1.49(m,1H),0.79(t,J=7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ141.61,138.22,137.77,134.55,134.24,129.66,129.19,129.09,1 29.03,128.80,128.00,126.89,80.98,45.22,31.70,30.08,12.05.HRMS(ESI-TOF)calculatedfor C 23 H 24 O4S2(MH + ):427.1043,found:427.1046. It was further confirmed that the molecular structure of the product was just as the above molecular structure 9.

[0209] Example 10

[0210] This embodiment provides a compound (Z)-ethyl 2-(((1-cyano-2-phenylpropylene)amino)oxy)acetate and a preparation method thereof. The structural formula of ethyl 2-(((1-cyano-2-phenylpropylene)amino)oxy)acetate is shown in the following molecular structural formula 10:

[0211]

[0212] The preparation method of ethyl ((Z)-2-(((1-cyano-2-phenylpropylidene)amino)oxy)acetate of the present embodiment comprises the following steps:

[0213] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent (0.2 mmol) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0214] The structure of the capture reagent is as follows:

[0215]

[0216] The structure of alkyl neopentylbenzene is as follows:

[0217]

[0218] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0219] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 43%.

[0220] The results of the relevant characterization analysis are 1 H NMR(500MHz,Chloroform-d)δ7.40–7.35(m,2H),7.34–7.27(m,3H),4.78(s,2H),4.27 (q,J=7.1Hz,2H),3.94(q,J=7.2Hz,1H),1.59(d,J=7.2Hz,3H),1.30(t,J=7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ168.40,139.01,137.72,129.07,127.91,127.50,109.29,71.71,61.34,42.56,17.96,14.16.HRMS(ESI-TOF)calculated for C 14 H 16 N2O3(M+H + ):261.1234,found:261.1234. This result further confirmed that the molecular structure of the product was just as the above molecular structure 10.

[0221] Embodiment 11

[0222] This embodiment provides a compound (Z)-N-ethoxy-2-phenylpropanecarboxylic acid cyanide and a preparation method thereof. The structural formula of (Z)-N-ethoxy-2-phenylpropanecarboxylic acid cyanide is shown in the following molecular structural formula 11:

[0223]

[0224] The preparation method of (Z)-N-ethoxy-2-phenylpropionic imide acyl cyanide of the present embodiment comprises the following steps:

[0225] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent (0.2 mmol) and the oxidant potassium persulfate (0.5 mmol) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0226] The structure of the capture reagent is as follows:

[0227]

[0228] The structure of alkyl neopentylbenzene is as follows:

[0229]

[0230] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0231] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 43%.

[0232] The results of the relevant characterization analysis are 1 H NMR(400MHz,Chloroform-d)δ7.43–7.29(m,7H),7.27–7.18(m,3H),4.34(q,J=7.1Hz,4H ),3.94(q,J=7.1Hz,1H),2.86(h,J=6.7Hz,1H),1.61(d,J=7.2Hz,6H),1.40–1.31(m,6H). 13 C NMR(101MHz,Chloroform-d)δ139.54,135.31,128.98,128.86,128.20,127.73,127. 43,127.02,125.74,109.88,71.87,42.44,18.09,14.34.HRMS(ESI-TOF)calculated for C 12 H 14 N2O(M+H + ):203.1179,found:203.1180. This result further confirmed that the molecular structure of the product was just as the above molecular structure 11.

[0233] Example 12

[0234] This embodiment provides a compound ((3aR, 4S, 5R, 6aS)-5-(benzoyloxy)-2-oxohexahydro-2H-cyclopenta[b]furan-4-yl)methyl 4-(((((Z)-1-cyano-2-phenylene)amino)oxy)methyl)benzoate and a preparation method thereof. The structural formula of ((3aR, 4S, 5R, 6aS)-5-(benzoyloxy)-2-oxohexahydro-2H-cyclopenta[b]furan-4-yl)methyl 4-(((((Z)-1-cyano-2-phenylene)amino)oxy)methyl)benzoate is shown in the following molecular structural formula 12:

[0235]

[0236] The preparation method of ((3aR, 4S, 5R, 6aS)-5-(benzoyloxy)-2-oxohexahydro-2H-cyclopenta[b]furan-4-yl)methyl 4-(((((Z)-1-cyano-2-phenylene)amino)oxy)methyl)benzoate of this embodiment comprises the following steps:

[0237] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent (0.2 mmol) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0238] The structure of the capture reagent is as follows:

[0239]

[0240] The structure of alkyl neopentylbenzene is as follows:

[0241]

[0242] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0243] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 60%.

[0244] The results of the relevant characterization analysis are 1H NMR(400MHz,Chloroform-d)δ8.09–7.97(m,4H),7.63–7.55(m,1H),7.51–7.41(m,4H),7.41–7.23(m,5H),5.51(dt,J=6.2,4.0Hz,1H),5.35(s,2H),5 .15(td,J=6.4,1.7Hz,1H),4.49–4.36(m,2H),3.93(q,J=7.1Hz,1H),3.06 –2.86(m,2H),2.73–2.57(m,3H),2.47–2.32(m,1H),1.59(d,J=7.2Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ176.08,165.94,165.90,141.69,139.07,137.01,133.39,129.87,129.69,129.42,129.36,129.04,128. 52,128.06,127.89,127.44,109.52,83.93,77.29,76.91,64.55,51.66,42.54,40.63,38.28,35.76,17.98.HRMS(ESI-TOF)calculated for C 12 H 14 N2O(M+H + ):567.2126,found:567.2127. This result further confirmed that the molecular structure of the product was just as the above molecular structure 12.

[0245] Embodiment 13

[0246] This embodiment provides a compound (3S, 5S, 8R, 9S, 10S, 13S, 14S)-10, 13-dimethyl-17-oxohexadecahydro-1H-cyclopenta[a]phenyl-3-yl-4-(((((Z)-1-cyano-2-phenylpropylidene)amino)oxy)methyl)benzoate and a preparation method thereof. The structural formula of (3S, 5S, 8R, 9S, 10S, 13S, 14S)-10, 13-dimethyl-17-oxohexadecahydro-1H-cyclopenta[a]phenyl-3-yl-4-(((((Z)-1-cyano-2-phenylpropylidene)amino)oxy)methyl)benzoate is shown in the following molecular structural formula 13:

[0247]

[0248] The preparation method of (3S,5S,8R,9S,10S,13S,14S)-10,13-dimethyl-17-oxohexadecahydro-1H-cyclopenta[a]phenyl-3-yl-4-(((((Z)-1-cyano-2-phenylpropylidene)amino)oxy)methyl)benzoate of the present embodiment comprises the following steps:

[0249] S01: The photocatalyst Mes-Acr-MeBF4 (0.01 mmol, 4.0 mg), the capture agent (0.2 mmol) and the oxidant ammonium persulfate (0.5 mmol, 114 mg) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0250] The structure of the capture reagent is as follows:

[0251]

[0252] The structure of alkyl neopentylbenzene is as follows:

[0253]

[0254] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0255] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 55%.

[0256] The results of the relevant characterization analysis are 1H NMR(400MHz,Chloroform-d)δ8.06(d,J=8.3Hz,2H),7.48–7.40(m,2H),7.40–7.34(m,2H),7.34–7.30(m,1H),7.28–7 .21(m,2H),5.34(s,2H),4.98(tt,J=11.4,4.9Hz,1H),3.91(q,J=7.1Hz,1H),2.52–2.40(m,1H),2.17–2.07(m,1H),1. 98(pd,J=8.6,7.3,4.2Hz,2H),1.88–1.77(m,4H),1.70(ddt,J=11.8,7.6,4.1Hz,2H),1.63–1.50(m,6H),1.45–1.29( m,6H),1.15(td,J=13.5,3.8Hz,1H),1.05(td,J=12.3,11.8,4.7Hz,1H),0.93(s,3H),0.90(s,3H),0.83–0.74(m,1H). 13 C NMR(101MHz,Chloroform-d)δ165.75,140.92,139.10,136.87,130.82,130. 12,129.78,129.43,129.01,127.90,127.83,127.43,109.54,74.26,54.35,5 1.39,47.79,44.74,42.53,36.77,35.85,35.73,35.07,34.06,31.56,30.84, 28.32,27.53,21.79,20.51,17.97,13.84,12.30.HRMS(ESI-TOF)calculated for C 37 H 44 N2O4(M+H + ):581.3374,found:581.3375. This result further confirmed that the molecular structure of the product was just as the above molecular structure 13.

[0257] Embodiment 14

[0258] This embodiment provides a compound 2-phenylpropionitrile and a preparation method thereof. The structural formula of 2-phenylpropionitrile is shown in the following molecular structural formula 14:

[0259]

[0260] The preparation method of the 2-phenylpropionitrile of the present embodiment comprises the following steps:

[0261] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent TsCN (0.2 mmol) and the oxidant sodium persulfate (0.5 mmol) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, and nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0262] The structure of alkyl neopentylbenzene is as follows:

[0263]

[0264] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0265] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 58%.

[0266] The results of the relevant characterization analysis are 1 H NMR (400MHz, Chloroform-d) δ7.47–7.31(m,5H),3.93(q,J=7.3Hz,1H),1.67(dd,J=7.4,1.5Hz,3H). 13 CNMR(101MHz,Chlorofo rm-d)δ137.10,129.15,128.05,126.71,121.60,31.26,21.47.HRMS(ESI-TOF)calculated for C9H9N(M+H + ):132.0808,found:132.0809. This result further confirmed that the molecular structure of the product is exactly the above-mentioned molecular structure 14.

[0267] Embodiment 15

[0268] This embodiment provides a compound (1-chloroethyl)benzene and a preparation method thereof. The structural formula of (1-chloroethyl)benzene is shown in the following molecular structural formula 15:

[0269]

[0270] The preparation method of (1-chloroethyl) benzene of the present embodiment comprises the following steps:

[0271] S01: The photocatalyst Mes-Acr-PhBF4 (0.01 mmol, 4.6 mg), the capture reagent TsCl (1.0 mmol,) and the oxidant sodium persulfate (0.5 mmol) were weighed into an oven-dried 8 mL vial equipped with a magnetic star bar, nitromethane and water (1 mL and 0.1 mL) were added, and then alkyl neopentylbenzene (0.2 mmol) was added to obtain a reaction solution.

[0272] The structure of alkyl neopentylbenzene is as follows:

[0273]

[0274] S02: The reaction vessel loaded with the reaction solution was degassed, backfilled with argon, and then placed under a 450nm Kessil lamp for irradiation (40W). The reaction progress was monitored by TLC to obtain a mixture containing the target product.

[0275] S03: The mixture was concentrated and purified by silica gel flash column chromatography to obtain the target product with a yield of 55%.

[0276] The results of the relevant characterization analysis are 1 H NMR (400MHz, Chloroform-d) δ7.54–7.45(m,2H),7.41(ddd,J=7.9,6.4,1.8Hz,2H),7.38–7.32(m,1H),5.15(q,J=6.8Hz,1H),1.91(dd,J=6.8,1.0Hz,3H). 13 CNMR(101MHz,Chloroform-d)δ142.85,128.66,128.26,126.53,58.80,26.56.HRMS(ESI-TOF)calculated for C8H9Cl(M+K + ):179.0024,found:179.0025. The molecular structure of the product was further confirmed as molecular structure 15.

[0277] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for generating and capturing photocatalytic alkyl radicals, characterized in that: The following steps are involved: The alkyl neopentylbenzene compound and the capture agent are subjected to a photocatalytic reaction under photocatalytic conditions; The method for photocatalytically reacting an alkyl neopentylbenzene compound and a capture agent under photocatalytic conditions comprises the following steps: The alkyl neopentylbenzene compound, the capture agent, the photocatalyst solution, the oxidant and the additive are mixed and treated, and a photocatalytic reaction is carried out under the irradiation of blue light; The general structural formula (I) of the alkyl neopentylbenzene compound is as follows: The R1 is an alkyl group, the R2 is any one of an alkyl group, an alkoxy group, a halogen group, a trifluoromethoxy group, and a hydrogen atom, the photocatalyst is Mes-Acr-PhBF4 or Mes-Acr-MeBF4, the oxidant is a persulfate, and the additive is water; The structure of the capture agent is any one of the following:

2. The method for generating and capturing photocatalytic alkyl radicals according to claim 1, characterized in that: The product structure of the photocatalytic reaction is as follows:

3. The method for generating and capturing photocatalytic alkyl radicals according to claim 1, characterized in that: The molar ratio of the photocatalyst, the oxidant and the additive is (0.1-20):(0.1-20):(0.2-40).

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