CN115710199A - Photo-oxidation-reduction catalysis method - Google Patents

Photo-oxidation-reduction catalysis method Download PDF

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CN115710199A
CN115710199A CN202211378442.0A CN202211378442A CN115710199A CN 115710199 A CN115710199 A CN 115710199A CN 202211378442 A CN202211378442 A CN 202211378442A CN 115710199 A CN115710199 A CN 115710199A
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radical
alkyl
group
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heteroaryl
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黄湧
陈杰安
廖柯
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Shenzhen Bay Laboratory Pingshan Biomedical R & D And Transformation Center
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Shenzhen Bay Laboratory Pingshan Biomedical R & D And Transformation Center
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    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract

The application relates to the technical field of synthetic chemistry, in particular to a photo-oxidation-reduction catalysis method. The photo-oxidation-reduction catalysis method comprises the following steps: providing a linear tertiary alcohol compound and a radical trapping reagent; and carrying out catalytic reaction on the linear tertiary alcohol compound and the free radical capture reagent under the condition of a photocatalyst. The application provides a new method for alcohol extension alkyl radical chemistry, under the condition of a photocatalyst, linear tertiary alcohol induces carbon-carbon bond fracture through single electron oxidation to generate alkyl radicals, and then the alkyl radicals are captured by a radical capture reagent to react to obtain various products; the photo-oxidation-reduction catalysis method obviously reduces the production cost for preparing the captured products, and greatly expands the designability and application prospect of the captured products.

Description

Photo-oxidation-reduction catalysis method
The application is a divisional application with the application number of 202110588659.3, the application date of 2021-05-28 and the name of the invention of 'photo-oxidation-reduction catalysis method'.
Technical Field
The application belongs to the technical field of synthetic chemistry, and particularly relates to a photo-oxidation-reduction catalysis method.
Background
In recent years, with the understanding of the mechanism of photocatalysis and the development of photo-oxidation-reduction catalysts, visible light-promoted photo-oxidation-reduction catalysis (photoredox catalysis) has been rapidly developed and achieved significant achievements, which have drastically changed modern radical chemistry.
Through research, alkyl free radicals play an indispensable role in the development of novel synthetic methods under photo/electrochemical catalysis. In general, alkyl radical precursors undergo a single electron transfer with the aid of a photoredox catalyst to generate transient alkyl radicals that can participate in various bond formation processes in a chemically and stereoselective manner, and a large number of alkyl radical precursors have been developed that have a built-in redox group that can narrow the energy gap between the excited states of the substrate and the photosensitizer. Despite the significant progress of the above studies, there has been little interest in generating alkyl radicals in a precisely controlled manner using common, environmentally friendly chemical feedstocks. The direct generation of alkyl radicals from simple, unactivated alcohols remains the first challenge in photo-redox catalysis due to the high oxidation potential of the alcohols.
Disclosure of Invention
The application aims to provide a photo-oxidation-reduction catalysis method, and aims to solve the technical problem of how to expand designable compounds by utilizing linear tertiary alcohol at low cost.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
a photo-redox catalysis method comprising the steps of:
providing a linear tertiary alcohol compound and a radical trapping reagent;
carrying out catalytic reaction on a linear tertiary alcohol compound and a free radical capture reagent under the conditions of a photocatalyst and blue light;
linear tertiary alcohol compounds include
Figure BDA0003927773300000021
Wherein n = an integer of 0 to 4, R 1 、R 2 And R 3 Are each independently selected from C 1 -C 20 Alkyl radical, C 1 -C 20 Heteroalkyl group, C 3 -C 20 Cycloalkyl, C 3 -C 20 Heterocycloalkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Heteroalkenyl, C 3 -C 20 CycloalkenesBase, C 3 -C 20 Heterocycloalkenyl, C 2 -C 20 Alkynyl, C 2 -C 20 Heteroalkynyl, C 3 -C 20 Cycloalkynyl group, C 3 -C 20 Heterocycloalkynyl, C 1 -C 20 Alkoxy radical, C 6 -C 14 Aryl, substituted (C) 6 -C 14 ) Aryl radical, C 4 -C 14 Heteroaryl, substituted (C) 4 -C 14 ) Heteroaryl group, C 6 -C 14 Aryloxy group, C 4 -C 14 Heteroaryloxy radical, C 6 -C 14 Aryl radical (C) 1 -C 20 ) Alkyl radical, C 4 -C 14 Heteroaryl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkenyl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkynyl (C) 1 -C 20 ) Alkyl, cyano (C) 1 -C 20 ) Alkyl radical, C 1 -C 20 Alkyloxycarbonyl (C) 1 -C 20 ) Alkyl radical, C 3 -C 20 Any one of alkyl silicon base, halogen, trifluoromethoxy, sulfonamide and hydrogen atom; and R is 2 And R 3 Is not a hydrogen atom; said substituted (C) 6 -C 14 ) Aryl and said substituted (C) 4 -C 14 ) The substituents in the heteroaryl group are independently selected from halogen atom and C 1 -C 5 Alkyl radical, C 1 -C 5 At least one of alkoxy, nitro and acyl;
the free radical capture reagent is selected from heterocyclic compounds, and the heterocyclic compounds are selected from at least one of quinoline, quinoline derivatives, pyridine derivatives, thiazole derivatives, benzothiazole derivatives, pyrazine derivatives, pyrimidine derivatives, purine and purine derivatives;
the photocatalyst is selected from acridine salt catalysts;
the photocatalysis reaction is also added with a Bronsted acid reagent, an oxidant and an acetonitrile solvent.
The photo-oxidation-reduction catalysis method is a new method for alcohol expansion alkyl radical chemistry, under the condition of a photocatalyst, linear tertiary alcohol induces carbon-carbon bond fracture through single electron oxidation to generate alkyl radicals, and the alkyl radicals are captured by a radical capture reagent to react to obtain various products; the photo-oxidation-reduction catalysis method obviously reduces the production cost for preparing the capture product, greatly expands the designability and application prospect of the capture product, and can be widely applied to the research fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicines.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. "at least one" means one or more, "plural" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The compounds and derivatives thereof referred to in the examples of this application are named according to the IUPAC (International Union of pure and applied chemistry) or CAS (chemical Abstract service, columbus, ohio) naming system. Accordingly, the groups of compounds specifically referred to in the examples of the present application are illustrated and described as follows:
with respect to "hydrocarbon group," the minimum and maximum values of the carbon atom content in a hydrocarbon group are indicated by a prefix, e.g., the prefix (Ca-Cb) alkyl indicates any alkyl group containing from "a" to "b" carbon atoms. Thus, for example, (C) 1 -C 6 ) Alkyl refers to alkyl groups containing one to six carbon atoms.
"alkoxy" refers to a straight or branched chain saturated aliphatic chain bonded to an oxygen atom, including but not limited to methoxy, ethoxy, propoxy, butoxy, isobutoxy, t-butoxy, and the like. (C) a -C b ) Alkoxy means any straight or branched, monovalent, saturated aliphatic chain in which an alkyl group containing "a" to "b" carbon atoms is bonded to an oxygen atom.
"alkyl" refers to a straight or branched chain saturated aliphatic chain, including but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and the like.
"heteroalkyl" means a saturated aliphatic chain, straight or branched, containing at least one heteroatom linkage, such as, but not limited to, methylaminoethyl, methyloxypropyl, or other similar groups.
"alkenyl" refers to straight or branched chain hydrocarbons having one or more double bonds, including but not limited to, groups such as ethenyl, propenyl, and the like.
"Heteroalkenyl" means a straight or branched chain hydrocarbon with one or more double bonds containing at least one heteroatom linkage, including but not limited to, for example, vinylaminoethyl or other similar groups.
"alkynyl" refers to a straight or branched chain hydrocarbon with one or more triple bonds, including but not limited to, for example, ethynyl, propynyl, and the like.
"Heteroalkynyl" refers to a straight or branched chain hydrocarbon with one or more triple bonds containing at least one heteroatom linkage.
"aryl" refers to a cyclic aromatic hydrocarbon, which may be monocyclic or polycyclic or fused, including but not limited to, for example, phenyl, naphthyl, anthryl, phenanthryl, and the like.
"heteroaryl" means a monocyclic or polycyclic or fused ring aromatic hydrocarbon in which one or more carbon atoms have been replaced with a heteroatom such as nitrogen, oxygen, or sulfur. If the heteroaryl group contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl groups include, but are not limited to, groups such as benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzopyranyl, furanyl, imidazolyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl, oxazinyl, oxazolyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridine [3,4-b ] indolyl, pyridyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolyl, quinoxalinyl, thiadiazolyl, thiatriazolyl, thiazolyl, thienyl, triazinyl, triazolyl, xanthenyl, and the like.
"cycloalkyl" refers to a saturated monocyclic or polycyclic alkyl group, possibly fused to an aromatic hydrocarbon group. Cycloalkyl groups include, but are not limited to, groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indanyl, tetrahydronaphthyl, and the like.
"Heterocycloalkyl" means a saturated monocyclic or polycyclic alkyl group in which at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different. Heterocycloalkyl groups include, but are not limited to, groups such as azepanyl, azetidinyl, indolinyl, morpholinyl, pyrazinyl, piperidinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydroquinolinyl, tetrahydroindazolyl, tetrahydroindolyl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydroquinoxalinyl, tetrahydrothiopyranyl, thiazolidinyl, thiomorpholinyl, thioxanthyl, and the like.
"cycloalkenyl" refers to an unsaturated monocyclic or polycyclic alkenyl group with one or more double bonds, possibly fused to an aromatic hydrocarbon group, including but not limited to, cyclic ethenyl, cyclopropenyl, or other similar groups.
"Heterocycloalkenyl" means an unsaturated monocyclic or polycyclic alkenyl group containing one or more double bonds, in which at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different.
"cycloalkynyl" refers to unsaturated monocyclic or polycyclic alkynyl groups having one or more triple bonds, possibly fused to aromatic hydrocarbon groups, including but not limited to cycloalkynyl, cyclopropynyl, or the like.
"Heterocycloalkynyl" means an unsaturated monocyclic or polycyclic alkynyl group having one or more triple bonds in which at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If a heterocyclic alkynyl group contains more than one heteroatom, these heteroatoms may be the same or different.
The hetero atom may be an oxygen atom, a nitrogen atom, a sulfur atom or the like.
"Tertiary alcohol" refers to tertiary alcohols, i.e., alcohols in which the hydroxyl group is replaced by a group having three non-hydrogen atoms. "linear tertiary alcohol" means that the carbon at the position of the hydroxyl group of the tertiary alcohol is in a linear or straight chain (linear), while the corresponding "cyclic tertiary alcohol" means that the carbon at the position of the hydroxyl group of the tertiary alcohol is in a cyclic chain (cyclic).
The embodiment of the application provides a photo-oxidation-reduction catalysis method, which comprises the following steps:
s01: providing a linear tertiary alcohol compound and a free radical trapping reagent;
s02: the linear tertiary alcohol compound and the free radical trapping reagent are subjected to catalytic reaction under the condition of a photocatalyst.
The photo-oxidation-reduction catalysis method is a new method for alcohol expansion alkyl radical chemistry, under the condition of a photocatalyst, linear tertiary alcohol induces carbon-carbon bond fracture through single electron oxidation to generate alkyl radicals, and the alkyl radicals are captured by a radical capture reagent to react to obtain various products; the photo-oxidation-reduction catalysis method obviously reduces the production cost for preparing the captured product, greatly expands the designability and application prospect of the captured product, is very easy to obtain the reactant raw materials, does not need to carry out additional modification on the reactant before reaction, can be directly used for preparation and production, simplifies the operation steps and shortens the reaction route; the production cost is obviously reduced, and the method can be widely applied to the fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicine research.
In the above-mentioned step S01,
linear tertiary alcohol compounds include
Figure BDA0003927773300000061
Wherein n = an integer of 0 to 4 (for example, n may be 0, 1,2, 3 or 4), R 1 、R 2 And R 3 Are each independently selected from C 1 -C 20 Alkyl radical, C 1 -C 20 Heteroalkyl group, C 3 -C 20 Cycloalkyl radical, C 3 -C 20 Heterocycloalkyl, C 2 -C 20 Alkenyl radical, C 2 -C 20 Heteroalkenyl, C 3 -C 20 Cycloalkenyl radical, C 3 -C 20 Heterocycloalkenyl, C 2 -C 20 Alkynyl, C 2 -C 20 Heteroalkynyl, C 3 -C 20 Cycloalkynyl group, C 3 -C 20 Heterocycloalkynyl, C 1 -C 20 Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C) 1 -C 20 ) Alkyl, heteroaryl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkenyl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkynyl (C) 1 -C 20 ) Alkyl, cyano (C) 1 -C 20 ) Alkyl radical, C 1 -C 20 Alkyloxycarbonyl (C) 1 -C 20 ) Alkyl radical, C 3 -C 20 Any one of alkyl silicon base, halogen, trifluoromethoxy, sulfonamide and hydrogen atom; and R is 2 And R 2 Not a hydrogen atom.
R 1 、R 2 And R 3 Are identical or different and are selected from C 1 -C 20 Alkyl radical, C 1 -C 20 Heteroalkyl group, C 3 -C 20 Cycloalkyl, C 3 -C 20 Heterocycloalkyl, C 2 -C 20 Alkenyl radical, C 2 -C 20 Heteroalkenyl, C 3 -C 20 Cycloalkenyl radical, C 3 -C 20 Heterocycloalkenyl, C 2 -C 20 Alkynyl, C 2 -C 20 Heteroalkynyl, C 3 -C 20 Cycloalkynyl group, C 3 -C 20 Heterocycloalkynyl, C 1 -C 20 Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C) 1 -C 20 ) Alkyl, heteroaryl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkenyl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkynyl (C) 1 -C 20 ) Alkyl, cyano (C) 1 -C 20 ) Alkyl radical, C 1 -C 20 Alkyloxycarbonyl (C) 1 -C 20 ) Alkyl radical, C 3 -C 20 The alkyl silyl, halogen (such as fluorine, chlorine, bromine and iodine), trifluoromethoxy, sulfonamide and hydrogen atom refer to R 1 、R 2 And R 3 Each independently selected from the above groups, which may be the same or different; and R is 2 And R 2 Not being hydrogenAnd (4) adding the active ingredients.
When R is 1 、R 2 Or R 3 Is selected from C 1 -C 20 Alkyl, in one embodiment, the (C) 1 -C 20 ) The alkyl group may be (C) 1 -C 10 ) Alkyl, (C) 1 -C 5 ) Alkyl, (C) 1 -C 4 ) Alkyl, (C) 1 -C 3 ) Alkyl, (C) 1 -C 2 ) Alkyl groups, and the like. In certain embodiments, (C) 1 -C 20 ) The alkyl group may be methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, and the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 1 -C 20 ) When it is heteroalkyl, in one embodiment, (C) is 1 -C 20 ) The heteroalkyl radical may be (C) 1 -C 10 ) Heteroalkyl group, (C) 2 -C 5 ) Heteroalkyl group, (C) 3 -C 4 ) Heteroalkyl groups and the like. In certain embodiments, the heteroatom may be an atom, a nitrogen atom, a sulfur atom, or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 3 -C 20 ) Cycloalkyl, in one embodiment, the (C) 3 -C 20 ) The cycloalkyl group may be (C) 3 -C 10 ) Cycloalkyl group, (C) 3 -C 5 ) Cycloalkyl group, (C) 3 -C 4 ) Cycloalkyl groups, and the like. In certain embodiments, (C) 3 -C 20 ) Cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl, and the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 3 -C 20 ) When it is heterocycloalkyl, in one embodiment, (C) is 3 -C 20 ) The heterocycloalkyl group may be (C) 3 -C 10 ) Heterocycloalkyl group, (C) 3 -C 10 ) Heterocycloalkyl group, (C) 3 -C 5 ) Heterocycloalkyl group, (C) 3 -C 4 ) Heterocycloalkyl, and the like. In certain embodiments, the heteroatom may be an oxygen atom, a nitrogen atom, a sulfur atom, and the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 2 -C 20 ) Alkenyl, in one embodiment, the (C) 2 -C 20 ) The alkenyl group may be (C) 3 -C 10 ) Alkenyl, (C) 3 -C 5 ) Alkenyl, (C) 3 -C 4 ) Alkenyl, (C) 2 -C 3 ) Alkenyl groups, and the like. In certain embodiments, (C) 2 -C 20 ) The alkenyl group may be ethenyl, propenyl, butenyl, pentenyl, etc.
When R is 1 、R 2 Or R 3 Is selected from (C) 2 -C 20 ) (iii) when heteroalkenyl, in one embodiment, the (C) 2 -C 20 ) Heteroalkenyl can be (C) 2 -C 10 ) Heteroalkenyl, (C) 3 -C 10 ) Heteroalkenyl, (C) 3 -C 5 ) Heteroalkenyl and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 3 -C 20 ) Cycloalkenyl, in one embodiment, the (C) 3 -C 20 ) Cycloalkenyl can be (C) 3 -C 10 ) Cycloalkenyl group, (C) 3 -C 5 ) Cycloalkenyl group, (C) 3 -C 4 ) Cycloalkenyl groups and the like. In certain embodiments, (C) 3 -C 20 ) Cycloalkenyl can be cyclopropenyl, cyclobutenyl, cyclopentenyl and the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 3 -C 20 ) When heterocycloalkenyl is present, in one embodiment, (C) is 3 -C 20 ) The heterocycloalkenyl can be (C) 3 -C 10 ) Heterocycloalkenyl, (C) 3 -C 5 ) Heterocycloalkenyl, (C) 3 -C 4 ) Heterocycloalkenyl, and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 2 -C 20 ) Alkynyl, in one embodiment, (C) 2 -C 20 ) Alkynyl may be (C) 2 -C 10 ) Alkynyl, (C) 3 -C 10 ) Alkynyl, (C) 3 -C 5 ) Alkynyl, (C) 3 -C 4 ) Alkynyl, (C) 2 -C 3 ) Alkynyl and the like. In certain embodiments, (C) 2 -C 20 ) The alkynyl group may be an ethynyl group, propynyl group, butynyl group, pentynyl group or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 2 -C 20 ) When heteroalkynyl is present, in one embodiment, (C) is 2 -C 20 ) Heteroalkynyl can be (C) 2 -C 10 ) Heteroalkynyl, (C) 3 -C 10 ) Heteroalkynyl, (C) 3 -C 5 ) Heteroalkynyl, (C) 3 -C 4 ) Heteroalkynyl, and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 3 -C 20 ) Cycloalkynyl is, in one embodiment, (C) is 3 -C 20 ) The cycloalkynyl group can be (C) 3 -C 10 ) Cycloalkynyl group, (C) 3 -C 5 ) Cycloalkynyl group, (C) 3 -C 4 ) Cycloalkynyl and the like. In certain embodiments, (C) 2 -C 20 ) The cycloalkynyl group may be cyclopropynyl, cyclobutynyl, cyclopentynyl, or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 3 -C 20 ) When heterocycloalkynyl is present, in one embodiment, (C) is 3 -C 20 ) The heterocycloalkynyl can be (C) 3 -C 10 ) Heterocycloalkynyl, (C) 3 -C 5 ) Heterocycloalkynyl, (C) 3 -C 4 ) Heterocycloalkynyl, and the like. In certain embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 1 -C 20 ) Alkoxy, in one embodiment, the (C) 1 -C 20 ) The alkoxy group may be (C) 1 -C 10 ) Alkoxy group, (C) 1 -C 8 ) Alkoxy group, (C) 1 -C 6 ) Alkoxy group, (C) 1 -C 4 ) Alkoxy group, (C) 1 -C 3 ) Alkoxy group, (C) 1 -C 2 ) An alkoxy group. In certain embodiments, this (C) 1 -C 20 ) Alkoxy groups can be, but are not limited to, methyloxy, ethyloxy, propyloxy, and the like.
When R is 1 、R 2 Or R 3 When selected from aryl, the aryl group can be, but is not limited to, monocyclic aryl, polycyclic aryl, fused ring aryl. In one embodiment, the aryl group is a monocyclic aryl group. In certain embodiments, the aryl group may be C 4 -C 14 Aryl groups such as phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and the like.
When R is 1 、R 2 Or R 3 When selected from substituted aryl groups, the substituted aryl groups may be, but are not limited to, phenyl substituted singly or multiply in the ortho, meta, or para positions. Substituents include, but are not limited to, alkyl, substituted alkyl, aryl, substituted aryl, acyl, halo, alkoxy, nitro. Wherein, when the substituent is an alkyl group, the alkyl group is exemplified by, but not limited to, methyl, ethyl, propyl, butyl, isobutyl; when the substituent is a substituted alkyl group, such as, but not limited to, trifluoromethyl, trichloromethyl, pentafluoroethyl, pentachloroethyl; when the substituent is halogen, such as, but not limited to, fluorine, chlorine, bromine, iodine; when the substituent is an alkoxy group, the alkoxy group is, for example, but not limited to, methyloxy, ethyloxy, propyloxy. In one embodiment, the substituted aryl group may be substituted (C) 4 -C 14 ) Aryl, e.g. being cyano (C) 1 -C 10 ) Alkyl radical (C) 4 -C 8 ) Aryl, substituted (C) 4 -C 8 ) And (4) an aryl group.
When R is 1 、R 2 Or R 3 When selected from heteroaryl, in one embodiment, the heteroaryl may be (C) 4 -C 14 ) Heteroaryl groups such as thienyl, thiazolyl, pyrrolyl, pyrazinyl, pyridyl, benzothiophene and the like.
When R is 1 、R 2 Or R 3 When selected from substituted heteroaryl, in one embodiment, the substituted heteroaryl may be substituted (C) 4 -C 14 ) Heteroaryl, e.g. alkoxy-substituted furans, (C) 3 -C 8 ) Heteroaryl substituted furans, aliphatic chain substituted thiophenes, and the like.
When R is 1 、R 2 Or R 3 When selected from aryloxy, in one embodiment, the aryloxyMay be C 4 -C 14 Aryloxy groups such as phenoxy, naphthoxy, anthracenoxy, phenanthrenoxy and the like.
When R is 1 、R 2 Or R 3 When selected from heteroaryloxy, in one embodiment, the heteroaryloxy group may be C 4 -C 14 A heteroaryloxy group.
When R is 1 、R 2 Or R 3 Selected from aryl (C) 1 -C 20 ) When it is an alkyl group, in one embodiment, the aryl group (C) 1 -C 20 ) The alkyl group may be C 4 -C 14 Aryl radical (C) 1 -C 10 ) Alkyl radicals, e.g. phenyl (C) 1 -C 10 ) Alkyl, phenyl (C) 1 -C 5 ) Alkyl, phenyl (C) 1 -C 4 ) Alkyl, phenyl (C) 1 -C 3 ) Alkyl, phenyl (C) 1 -C 2 ) Alkyl groups, and the like. In certain embodiments, aryl (C) 1 -C 20 ) The alkyl group may be phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylisobutyl, phenylpentyl, phenylisopentyl, phenylneopentyl, and the like.
When R is 1 、R 2 Or R 3 Is selected from heteroaryl (C) 1 -C 20 ) When alkyl, in one embodiment, the heteroaryl (C) 1 -C 20 ) The alkyl group may be C 4 -C 14 Heteroaryl (C) 1 -C 10 ) Alkyl radicals, e.g. heteroaryl (C) 1 -C 10 ) Alkyl, heteroaryl (C) 1 -C 5 ) Alkyl, heteroaryl (C) 1 -C 4 ) Alkyl, heteroaryl (C) 1 -C 3 ) Alkyl, heteroaryl (C) 1 -C 2 ) Alkyl groups, and the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 2 -C 20 ) Alkenyl (C) 1 -C 20 ) When it is an alkyl group, in one embodiment, the group (C) 2 -C 20 ) Alkenyl (C) 1 -C 20 ) The alkyl group may be (C) 2 -C 10 ) Alkenyl (C) 1 -C 10 ) Alkyl, (C) 2 -C 5 ) Alkenyl (C) 1 -C 3 ) Alkyl groups, and the like.
When R is 1 、R 2 Or R 3 Is selected from (C) 2 -C 20 ) Alkynyl (C) 1 -C 20 ) When it is an alkyl group, in one embodiment, the group (C) 2 -C 20 ) Alkynyl (C) 1 -C 20 ) The alkyl group may be (C) 2 -C 10 ) Alkynyl (C) 1 -C 10 ) Alkyl, (C) 2 -C 5 ) Alkynyl (C) 1 -C 3 ) Alkyl groups, and the like.
When R is 1 、R 2 Or R 3 Is selected from cyano (C) 1 -C 20 ) Alkyl, in one embodiment, the cyano (C) 1 -C 20 ) The alkyl group may be cyano (C) 1 -C 10 ) Alkyl, cyano (C) 1 -C 5 ) Alkyl, cyano (C) 1 -C 4 ) Alkyl, cyano (C) 1 -C 3 ) Alkyl, cyano (C) 1 -C 2 ) Alkyl groups, and the like. In certain embodiments, cyano (C) 1 -C 20 ) The alkyl group may be cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, or the like.
When R is 1 、R 2 Or R 3 Is selected from C 3 -C 20 When alkylsilyl, in one embodiment, C 3 -C 20 The alkylsilyl group may be C 3 -C 18 Alkylsilyl, C 3 -C 10 Alkylsilyl, C 3 -C 5 Alkylsilyl groups, and the like.
When R is 1 、R 2 Or R 3 Is selected from C 1 -C 20 Alkyloxycarbonyl (C) 1 -C 20 ) When it is alkyl, in one embodiment, the C 1 -C 20 Alkyloxycarbonyl (C) 1 -C 20 ) The alkyl group may be (C) 1 -C 10 ) Alkyloxycarbonyl (C) 1 -C 10 ) Alkyl, (C) 1 -C 5 ) Alkyloxycarbonyl (C) 1 -C 5 ) Alkyl, (C) 1 -C 4 ) Alkyloxycarbonyl (C) 1 -C 4 ) Alkyl groups, and the like.
The above-mentioned radical trapping reagent may be selected from at least one of an electron-deficient alkenyl-containing compound, a heterocyclic compound, and a thifluorotrifluoromethyl radical precursor, for example, the present application is selected from a heterocyclic compound. The linear tertiary alcohols that are not activated in the present application are oxidized by the photocatalyst, and the resulting alkoxy groups selectively undergo β -scission to deliver alkyl radicals that can be accepted by various nucleophiles to be captured by the above-mentioned radical trapping agents for addition or substitution to give products.
Specifically, the electron-deficient alkenyl-containing compound of the radical trapping reagent is selected from at least one of benzylallyldinitrile, 1-bis (phenylsulfonyl) ethylene, methyl 2-phenylacrylate, and 2-vinylpyridine; the compound containing electron-deficient alkenyl and linear tertiary alcohol compound are subjected to catalytic reaction to obtain a primary alkyl free radical, a secondary alkyl free radical or a tertiary alkyl free radical and the addition product of the compound containing electron-deficient alkenyl, such as the benzyl allyl dinitrile, 1-bis (phenylsulfonyl) ethylene, 2-methyl phenyl acrylate, 2-vinylpyridine and the like.
Alternatively, the heterocyclic compound of the radical capturing agent is a heterocyclic compound containing a nitrogen atom, such as at least one selected from the group consisting of quinoline, quinoline derivatives, pyridine derivatives, thiazole derivatives, benzothiazole derivatives, pyrazine derivatives, pyrimidine derivatives, purine and purine derivatives; the heterocyclic compound and the linear tertiary alcohol compound are subjected to catalytic reaction to obtain a primary alkyl free radical, a secondary alkyl free radical or a tertiary alkyl free radical, and the heterocyclic compound reacts to generate a mono-substituted alkyl substitution product. Further, the quinoline derivatives may be alkyl or other group-substituted quinolines, such as 2-methylquinoline, quinine, etc.; the above-mentioned pyridine derivative may be alkyl-or other group-substituted pyridine, such as 2, 6-lutidine, etc.; the thiazole derivative may be a thiazole substituted with an alkyl group or other group, such as ethyl 5-methylthiazole-4-carboxylate, etc.; the pyrazine derivatives may be alkyl or pyrazine substituted with other groups, such as 2,3, 5-trimethylpyrazine and the like; the above pyrimidine derivative may be alkyl or other group-substituted pyrimidine, such as 4, 6-dimethylpyrimidine; the purine derivatives may be alkyl or other substituted purines, such as 2, 6-dichloro-9-methyl-9H-purine.
Or the sulfur trifluoromethyl radical precursor of the radical trapping reagent is selected from N- (trifluoromethylthio) phthalimide, so that the sulfur trifluoromethyl radical precursor and the linear tertiary alcohol compound are subjected to catalytic reaction to obtain the corresponding sulfur trifluoromethyl substituted alkyl product.
The linear tertiary alcohol compound functions as a nucleophile and is capable of attacking at least one of the electron-deficient alkenyl-containing compound, the heterocyclic compound, and the thifluorotrifluoromethyl radical precursor to cause reaction of the two reactants. Therefore, the atom utilization rate of reactants is effectively improved, and the limitation of a substrate can be widened, so that a target product precursor with high enantioselectivity and extremely wide range is efficiently and greenly prepared, and a product with potential application value is obtained through a simple reduction reaction.
In one embodiment, the photocatalyst is an acridine salt catalyst as shown below;
Figure BDA0003927773300000111
wherein X is a tetrafluoroborate anion, a hexafluorophosphate anion or a perchlorate anion; r is 4 、R 5 And R 6 Are each independently selected from C 1 -C 20 Alkyl radical, C 1 -C 20 Heteroalkyl group, C 3 -C 20 Cycloalkyl radical, C 3 -C 20 Heterocycloalkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Heteroalkenyl, C 3 -C 20 Cycloalkenyl radical, C 3 -C 20 Heterocycloalkenyl, C 2 -C 20 Alkynyl, C 2 -C 20 Heteroalkynyl, C 3 -C 20 Cycloalkynyl group, C 3 -C 20 Heterocycloalkynyl, C 1 -C 20 Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C) 1 -C 20 ) Alkyl, heteroaryl (C) 1 -C 20 ) Alkyl, (C) 2 -C 20 ) Alkenyl (C) 1 -C 20 ) Alkyl, (C) 2 -C 20 ) Alkynyl (C) 1 -C 20 ) Alkyl and cyano (C) 1 -C 20 ) Any one of alkyl groups. The catalyst has better photo-oxidation-reduction catalysis effect. In a preferred embodiment of the present application, the photocatalyst is selected from the group consisting of Mes-Acr-PhBF 4 。
Further, at least one of a Bronsted acid reagent and an oxidizing agent is added in the catalytic reaction. Specifically, the two are added, and the photocatalyst, the oxidant and the Bronsted acid reagent act synergistically, so that the catalytic system is low in toxicity, the atom utilization rate and the reaction efficiency are improved, and byproducts are few; meanwhile, the reaction process is safe and controllable, and the operation in the preparation production process is simplified. The photocatalyst can provide a better single-electron oxidation effect, so that the carbon-carbon bond breaking efficiency is improved in the catalytic reaction process; oxidizing agents and Bronsted acid reagents are used for the addition reaction of free radicals to heterocycles. Specifically, the bronsted acid reagent is selected from at least one of acetic acid, fluoroacetic acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, and nitric acid; the oxidant is at least one selected from the group consisting of a high-valent iodine compound, a peroxy compound, a quinone compound, a persulfate, potassium permanganate, oxygen, and N-fluorobenzenesulfonylimide.
The contents of the three components are in a certain range under a certain proportion condition, so that the reaction has higher catalytic efficiency, and a target product with higher yield is obtained. Specifically, the molar ratio of the photocatalyst, the oxidant and the Bronsted acid reagent is (0.1-20): (0.2-40). In the proportion, the reaction has high catalytic efficiency, and the yield of the reaction product is improved. Preferably, the molar ratio of the photocatalyst to the oxidizing agent to the Bronsted acid reagent is (0.2-20): 2.5 (1-10), in this case, the target product with the highest yield is obtained.
In one embodiment, the catalytic reaction is carried out by dissolving a linear tertiary alcohol compound and a radical trapping reagent in an acetonitrile solution; further, the catalytic reaction is carried out under blue light conditions. For example, linear tertiary alcohol and a radical capture reagent are added into an acetonitrile solution containing an acridinium salt photocatalyst and react under blue light irradiation to obtain a product after the alkyl radical and the capture reagent are added, and the additive can comprise a Bronsted acid reagent and an oxidizing agent.
The linear tertiary alcohol compound is oxidized through single electron transfer, so that the linear tertiary alcohol compound is induced to generate carbon-carbon bond breakage and then reacts with a free radical capture reagent; has the following advantages: through the carbon-carbon bond breakage of linear tertiary alcohol, the substrate range is wider, and the generated alkyl free radical can be captured by various free radical capture reagents. It is worth noting that quinine which is widely applied in asymmetry and medicine can be well modified, the reaction process is safe and controllable, and the operation in the preparation and production process is simplified. In addition, the method obviously reduces the production cost for preparing the captured product, and greatly expands the designability and application prospect of the compound. The addition product obtained by the method has high functional group, is more diversified in the synthesis of a drug intermediate, the application of a functional material and a metal ligand, can be widely used for the synthesis of the drug intermediate and the preparation of a chiral ligand and a functional material, can effectively reduce the economic cost for the preparation of the drug intermediate and the functional material, and provides environmental friendliness. The fragmentation method and the captured product provided by the application have high functional group property, and can be widely applied to the research fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicines, such as the synthesis of pharmaceutical intermediates, particularly compounds containing the quaternary carbon center structure and the preparation field of functional materials.
The method comprises the step of carrying out photo-oxidation-reduction catalytic reaction on different linear tertiary alcohol compounds and different free radical capture reagents to obtain different products. Specifically, the examples of the present application provide the photo-oxidation-reduction catalysis method, which uses different raw materials to obtain the following 21 products.
Figure BDA0003927773300000131
The compound obtained by the photocatalysis method can be used for synthesis of drug intermediates and preparation of functional materials and metal ligands, so that the preparation method has good application prospect.
The following description is given with reference to specific examples.
Example 1
A method for preparing 2- (1, 2-diphenyl ethyl) malononitrile compound (structural formula is shown as formula 1 below):
Figure BDA0003927773300000141
the photocatalyst Mes-Acr-PhBF is added 4 (0.01mmol, 4.6 mg) and the capture reagent benallyldinitrile (0.4mmol, 61.7 mg) were weighed into an oven-dried 8mL vial equipped with a magnetometric star marker rod. Anhydrous acetonitrile (1 mL) was added followed by linear tertiary alcohol (2-methyl-1-phenyl-2-propanol) (0.2 mmol). The reaction vessel was degassed, backfilled with argon, and then placed in a SynLED4x4 photoreactor (SynLED discover (tm) 450nm, designed and manufactured by shenzhen SynLED tech. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 85% yield.
Correlation characterization analysis, the result is 1 H NMR(500MHz,Chloroform-d)δ7.47–7.38(m,5H),7.35(dd,J＝8.1,6.4Hz,2H),7.32–7.28(m,1H),7.24–7.17(m,2H),3.86(d,J＝5.1Hz,1H),3.48(ddd,J＝8.6,7.2,5.1Hz,1H),3.35–3.22(m,2H). 13 C NMR(126MHz,Chloroform-d)δ136.66,136.46,129.23,129.18,129.10,128.94,128.05,127.61,112.07,111.46,48.40,38.57,28.56.HRMS(ESI-TOF)calculated for C 17 H 14 N 2 (M+Na + ) 269.1049, found.
Example 2
A method for preparing 2- (1, 3-diphenyl propyl) malononitrile compound (structural formula is shown as the following formula 2):
Figure BDA0003927773300000151
the linear tertiary alcohol is 3-methyl-1-phenyl-3-pentanol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 1 was repeated, yielding 81%.
Correlation characterization analysis, the result is 1 H NMR(500MHz,Chloroform-d)δ7.51–7.40(m,3H),7.38–7.28(m,4H),7.26–7.22(m,1H),7.14–7.07(m,2H),3.86(d,J＝6.2Hz,1H),3.20(dt,J＝10.2,5.7Hz,1H),2.66(ddd,J＝13.6,8.3,5.2Hz,1H),2.48(dt,J＝13.8,8.2Hz,1H),2.43–2.29(m,2H). 13 C NMR(126MHz,Chloroform-d)δ139.90,136.24,129.48,129.12,128.73,128.38,128.05,126.57,111.81,111.77,45.64,33.53,32.77,30.37.HRMS(ESI-TOF)calculated for C 18 H 16 N 2 (M+Na + ) 283.1206, found 283.1206, the result further confirms that the molecular structure of the product is just like the molecular structure 2.
Example 3
A method for preparing 2- (2- (4-isobutylphenyl) -1-phenylpropyl) malononitrile compound (structural formula is shown as formula 3 below):
Figure BDA0003927773300000152
the linear tertiary alcohol is 3- (4-isobutylphenyl) -2-methylbutan-2-ol, and the capture reagent is benzyl allyl dinitrile; otherwise the same procedure as in example 1 was followed, with a yield of 84%, dr 1.
Correlation characterization analysis, which resulted in isomer 1: 1 H NMR(500MHz,Chloroform-d)δ7.31–7.22(m,3H),7.01–6.90(m,4H),6.84(d,J＝7.9Hz,2H),4.07(d,J＝8.1Hz,1H),3.49(p,J＝7.0Hz,1H),3.42(t,J＝7.8Hz,1H),2.40(dd,J＝7.2,1.8Hz,2H),1.80(dp,J＝13.5,6.8Hz,1H),1.43(d,J＝6.9Hz,3H),0.86(dd,J＝6.6,1.5Hz,6H). 13 C NMR(126MHz,Chloroform-d)δ140.84,137.54,134.88,129.12,128.85,128.57,128.46,127.87,112.58,112.03,52.76,44.95,41.25,30.15,27.48,22.35,22.28,19.93.
isomer 2: 1 H NMR(400MHz,Chloroform-d)δ7.58–7.42(m,5H),7.30(d,J＝7.9Hz,2H),7.23(d,J＝8.1Hz,2H),3.65(d,J＝4.1Hz,1H),3.40(dq,J＝11.5,6.8Hz,1H),3.20(dd,J＝11.7,4.1Hz,1H),2.53(d,J＝7.2Hz,2H),1.92(dp,J＝13.5,6.7Hz,1H),1.16(d,J＝6.8Hz,3H),0.96(d,J＝6.6Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ141.68,139.53,135.66,130.33,129.26,129.07,128.57,126.78,112.27,111.52,53.74,45.02,41.65,30.19,28.73,22.43,22.41,20.59.HRMS(ESI-TOF)calculated for C 22 H 24 N 2 (M-H + ) 315.1867, found.
Example 4
A method for preparing 2- (1, 2-diphenylbutyl) malononitrile compound (structural formula is shown as formula 4 below):
Figure BDA0003927773300000161
the linear tertiary alcohol is 2-methyl-3-phenylpentane-2-ol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 1 was repeated, wherein the yield was 93%, and dr was 1.
Correlation characterization analysis, which resulted in isomer 1: 1 H NMR(400MHz,Chloroform-d)δ7.34–7.26(m,3H),7.23(dd,J＝5.2,1.9Hz,3H),7.00–6.84(m,4H),4.06(d,J＝8.7Hz,1H),3.57(dd,J＝8.7,7.1Hz,1H),3.26(ddd,J＝10.5,7.1,4.7Hz,1H),1.89(dtd,J＝14.5,7.3,4.7Hz,1H),1.78–1.64(m,1H),0.86(t,J＝7.3Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ138.03,134.70,129.05,128.85,128.60,128.46,128.37,127.41,112.60,111.96,51.41,49.07,27.39,26.51,11.97.
isomer 2: 1 H NMR(400MHz,Chloroform-d)δ7.59–7.42(m,7H),7.42–7.33(m,3H),3.61(d,J＝4.1Hz,1H),3.30(dd,J＝11.8,4.1Hz,1H),3.15(td,J＝11.4,3.4Hz,1H),1.65–1.38(m,2H),0.65(t,J＝7.3Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ140.23,135.80,129.64,129.33,129.11,128.52,128.11,127.91,112.17,111.46,52.67,49.60,28.81,27.03,12.02.HRMS(ESI-TOF)calculated for C 19 H 18 N 2 (M-H + ) 273.1397, found 273.1399. This result further confirms the molecular structure of the product as that of molecular structure 4 above.
Example 5
A method for preparing 2- (2-methoxy-1-phenylethyl) malononitrile compound (structural formula is shown in the following formula 5):
Figure BDA0003927773300000171
the photocatalyst Mes-Acr-PhBF is added 4 (0.01mmol, 4.6 mg) and the capture reagent benallyldinitrile (0.2mmol, 30.8 mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Anhydrous acetonitrile (1 mL) was added followed by linear tertiary alcohol (1-methoxy-2-phenylpropan-2-ol) (0.24 mmol). The reaction vessel was degassed, backfilled with argon and then placed in a SynLED4x4 photoreactor (SynLED discover (tm) 450 nm). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 92% yield.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ7.51–7.33(m,5H),4.44(d,J＝6.0Hz,1H),3.91–3.76(m,2H),3.48(m,4H). 13 C NMR(101MHz,Chloroform-d)δ134.46,129.26,128.16,112.12,111.63,71.58,59.34,46.43,26.30.HRMS(ESI-TOF)calculated for C 12 H 12 N 2 O(M-H + ) 199.0877, found.
Example 6
A method for preparing a 2- (phenyl (tetrahydro-2H-pyran-4-yl) methyl) malononitrile compound (structural formula is shown in the following formula 6):
Figure BDA0003927773300000172
the linear tertiary alcohol is 1-phenyl-1- (tetrahydro-2H-pyran-4-yl) ethan-1-ol, and the capture reagent is benzyl allyl dinitrile; the other preparation was the same as in example 5, and the yield was 94%.
Correlation characterization analysis, the result of which is 1 H NMR(500MHz,Chloroform-d)δ7.47–7.37(m,3H),7.37–7.32(m,2H),4.17(d,J＝5.0Hz,1H),4.13–4.05(m,1H),3.95–3.85(m,1H),3.49(td,J＝11.9,2.3Hz,1H),3.34(td,J＝11.8,2.3Hz,1H),2.91(dd,J＝10.2,5.0Hz,1H),2.28(dddt,J＝11.6,10.2,7.6,3.8Hz,1H),1.82(ddd,J＝12.6,4.0,2.1Hz,1H),1.49(qd,J＝12.1,4.6Hz,1H),1.32(ddq,J＝13.6,4.5,2.3Hz,1H),1.22(dtd,J＝13.4,11.7,4.5Hz,1H). 13 C NMR(126MHz,Chloroform-d)δ135.77,129.38,129.13,128.25,111.81,111.67,67.56,67.14,52.01,37.03,31.10,30.70,26.85.HRMS(ESI-TOF)calculated for C 15 H 16 N 2 O(M-H + ) 239.1190, found.
Example 7
A method for preparing 2- (1-phenyl dodecyl) malononitrile compound (structural formula is shown as formula 7 below):
Figure BDA0003927773300000181
the linear tertiary alcohol is 2-phenyl-tridecyl-2-alcohol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was followed, giving a yield of 77%.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ7.48–7.36(m,3H),7.36–7.30(m,2H),3.90(d,J＝6.2Hz,1H),3.22(dt,J＝8.9,6.5Hz,1H),2.02(td,J＝8.3,5.9Hz,2H),1.42–1.17(m,18H),0.91(t,J＝6.8Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ136.84,129.27,128.85,127.82,111.93,46.61,32.11,31.89,30.27,29.57,29.54,29.45,29.31,29.25,29.13,26.96,22.68,14.12.HRMS(ESI-TOF)calculated for C 21 H 30 N 2 (M-H + ) 309.2336, found 309.2338. This result further confirmed that the molecular structure of the product was as described above for molecular structure 7.
Example 8
A method for preparing a 2- ((4, 4-difluorocyclohexyl) (phenyl) methyl) malononitrile compound (structural formula is shown as the following formula 8):
Figure BDA0003927773300000182
the linear tertiary alcohol is 1- (4, 4-difluorocyclohexyl) -1-phenylethane-1-ol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was repeated, yielding 76%.
Correlation characterization analysis, the result of which is 1 H NMR(400MHz,Chloroform-d)δ7.51–7.39(m,3H),7.39–7.31(m,2H),4.19(d,J＝5.2Hz,1H),2.98(dd,J＝9.9,5.2Hz,1H),2.25(ttt,J＝10.7,7.3,3.7Hz,1H),2.19–2.10(m,1H),2.04(ddt,J＝13.9,7.2,3.5Hz,2H),1.89(dtt,J＝34.9,13.7,4.0Hz,1H),1.80–1.60(m,1H),1.60–1.43(m,2H),1.33–1.19(m,1H). 13 C NMR(101MHz,Chloroform-d)δ136.16,129.46,129.19,127.96,111.65,51.21,37.67,33.02(t,J＝24.0Hz),27.52,27.23(d,J＝9.9Hz),26.82(d,J＝9.7Hz). 19 F NMR(376MHz,Chloroform-d)δ-93.10(d,J＝237.2Hz),-103.04(d,J＝237.6Hz).HRMS(ESI-TOF)calculated for C 16 H 16 F 2 N 2 (M-H + ) 273.1209, found 273.1210, the results further confirm the molecular structure of the product as that of molecular structure 8 above.
Example 9
A process for producing a 2- (((3r, 5r, 7r) -adamantan-1-yl) (phenyl) methyl) malononitrile compound (structural formula shown in the following formula 9):
Figure BDA0003927773300000191
the linear tertiary alcohol is 1- ((3r, 5r, 7r) -adamantan-1-yl) -1-phenylethane-1-alcohol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was followed, giving a yield of 85%.
Correlation characterization analysis, the result is 1 H NMR(500MHz,Chloroform-d)δ7.39(m,J＝7.5Hz,5H),4.26(d,J＝5.4Hz,1H),2.82(d,J＝5.3Hz,1H),2.04(q,J＝3.2Hz,3H),1.77–1.65(m,9H),1.61(m,3H). 13 C NMR(126MHz,Chloroform-d)δ135.34,129.70,128.63,128.57,113.48,113.33,58.09,40.44,36.58,36.39,28.43,23.79.HRMS(ESI-TOF)calculated for C 20 H 22 N 2 (M-H + ) 289.1710, found 289.1709. The results further confirm the molecular structure of the product as in molecular structure 9 above.
Example 10
A method for preparing 2- (2- (allyloxy) -1-phenylethyl) malononitrile compound (formula is shown as formula 10 below):
Figure BDA0003927773300000201
the linear tertiary alcohol was 1- (allyloxy) -2-phenylpropan-2-ol and the capture reagent was benzylallyldinitrile, the procedure was otherwise the same as in example 5, in 68% yield.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ7.43(tdd,J＝7.2,5.6,2.1Hz,5H),5.95(ddt,J＝17.3,10.4,5.7Hz,1H),5.43–5.20(m,2H),4.48(d,J＝5.8Hz,1H),4.12(dt,J＝5.7,1.4Hz,2H),3.95–3.77(m,2H),3.51(ddd,J＝8.7,5.8,4.7Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ134.46,133.59,129.26,128.18,118.25,112.14,111.64,72.55,69.02,46.51,26.39.HRMS(ESI-TOF)calculated for C 14 H 14 N 2 O(M-H + ) 225.1033, found 225.1028 the results further confirm that the molecular structure of the product is just like the molecular structure 10 described above.
Example 11
A method for preparing 4-isopropyl-2-methylquinoline compound (structural formula is shown as formula 11 below):
Figure BDA0003927773300000202
the photocatalyst Mes-Acr-PhBF is added 4 (0.01mmol, 4.6 mg), ammonium persulfate (0.5 mmol) and capture reagent heterocyclic 2-methylquinoline (0.2 mmol) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Addition of H 2 O (0.1 mL) and MeCN (0.9 mL), followed by the addition of the linear tertiary alcohol 3-methyl-2-phenylbutan-2-ol (0.4 mmol) and then trifluoroacetic acid (0.4 mmol). Degassing the reaction vessel and usingArgon was backfilled and then placed in a SynLED4x4 photoreactor (SynLED discover (tm) 450 nm). The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was quenched with 1N NaOH (10 mL). The combined organic layers were washed with brine and dried (Na) 2 SO 4 ) And concentrated in vacuo. The crude product was purified by flash column on silica gel. Compound 11 was produced in 78% yield.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ8.15–7.96(m,2H),7.68(ddd,J＝8.5,6.9,1.4Hz,1H),7.52(ddd,J＝8.2,6.9,1.4Hz,1H),7.21(s,1H),3.73(p,J＝6.9Hz,1H),2.76(s,3H),1.42(d,J＝6.9Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ158.83,154.30,148.07,129.50,128.82,125.34,125.15,122.90,117.75,28.22,25.55,22.93.HRMS(ESI-TOF)calculated for C 13 H 15 N(M+H + ) 186.1277, found.
Example 12
A method for preparing 2-benzyl-3, 5, 6-trimethylpyrazine compound (structural formula is shown as formula 12 below):
Figure BDA0003927773300000211
the linear tertiary alcohol was 2-methyl-1-phenyl-2-propanol, and the trapping reagent was 2,3, 5-trimethylpyrazine, which was otherwise the same as the preparation method of example 11, and the yield was 67%.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ7.35–7.25(m,2H),7.24–7.13(m,3H),4.16(s,2H),2.54(s,3H),2.51(s,3H),2.44(s,3H). 13 C NMR(101MHz,Chloroform-d)δ150.14,148.96,148.58,148.55,138.48,128.57,128.44,126.29,41.19,21.54,21.50,21.27.HRMS(ESI-TOF)calculated for C 14 H 16 N 2 (M+H + ) 213.1386, found 213.1386. The results further confirm that the molecular structure of the product is as in the molecular structure 12 described above.
Example 13
A method for preparing a 2-isopropylbenzo [ d ] thiazole compound (structural formula is shown in the following formula 13):
Figure BDA0003927773300000212
the linear tertiary alcohol is 3-methyl-2-phenylbutane-2-ol, and the capture reagent is benzothiazole; otherwise, the same procedure as in example 11 was repeated, giving a yield of 83%.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ8.01(d,J＝8.2Hz,1H),7.88(d,J＝8.0Hz,1H),7.48(t,J＝7.7Hz,1H),7.37(t,J＝7.6Hz,1H),3.46(p,J＝6.9Hz,1H),1.52(d,J＝6.9Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ178.64,153.11,134.68,125.84,124.58,122.57,121.55,34.10,22.91.HRMS(ESI-TOF)calculated for C 10 H 11 NS(M+H + ) 178.0685, found 178.0685. The results further confirm the molecular structure of the product as in the above molecular structure 13.
Example 14
A method for preparing 4-cyclohexyl-2, 6-dimethylpyridine compound (structural formula is shown as formula 14 below):
Figure BDA0003927773300000221
the linear tertiary alcohol is 1-cyclohexyl-1-phenylethane-1-alcohol, and the capture reagent is 2, 6-dimethylpyridine; otherwise, the same procedure as in example 11 was followed, giving a yield of 51%.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ6.82(s,2H),2.52(s,6H),2.44(dq,J＝8.8,5.8,4.2Hz,1H),1.95–1.81(m,4H),1.81–1.73(m,1H),1.49–1.33(m,4H),1.33–1.19(m,1H). 13 C NMR(101MHz,Chloroform-d)δ157.43,157.21,118.91,43.85,33.56,26.60,26.01,24.42.HRMS(ESI-TOF)calculated for C 13 H 19 N(M+H + ) 190.1590, found 190.1589 this result further confirms the molecular structure of the product as that of molecular structure 14 described above.
Example 15
A method for preparing 2-cyclopentyl-4, 6-dimethylpyrimidine compound (structural formula is shown as formula 15 below):
Figure BDA0003927773300000222
the linear tertiary alcohol is 1-cyclopentyl-1-phenylethane-1-alcohol, and the capture reagent is 4, 6-dimethylpyrimidine; otherwise, the same procedure as in example 11 was followed, giving a yield of 56%.
Correlation characterization analysis, the result is 1 H NMR(500MHz,Chloroform-d)δ6.83(s,1H),3.26(p,J＝8.4Hz,1H),2.45(s,6H),2.14–2.00(m,2H),1.98–1.80(m,4H),1.76–1.62(m,2H). 13 C NMR(126MHz,Chloroform-d)δ173.70,166.29,117.25,48.98,33.07,25.95,24.05.HRMS(ESI-TOF)calculated for C 11 H 16 N 2 (M+H + ) 177.1386, found 177.1386. The results further confirm the molecular structure of the product as in the molecular structure 15 above.
Example 16
A method for preparing 2-isopropyl-5-methylthiazole-4-carboxylic acid ethyl ester compound (structural formula is shown in the following formula 16):
Figure BDA0003927773300000231
the linear tertiary alcohol is 3-methyl-2-phenylbutane-2-ol, and the capture reagent is 5-methylthiazole-4-carboxylic acid ethyl ester; otherwise, the same procedure as in example 11 was followed, giving a yield of 61%.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ4.42(q,J＝7.1Hz,2H),3.36(p,J＝6.9Hz,1H),2.74(s,3H),1.42(t,J＝7.1Hz,3H),1.38(d,J＝6.9Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ174.06,162.68,143.60,140.41,61.01,33.45,23.34,14.45,13.27.HRMS(ESI-TOF)calculated for C 10 H 15 NO 2 S(M+H + ) 214.0896, found 214.0896, the results further confirm the molecular structure of the product as in the molecular structure 16 described above.
Example 17
A method for preparing 2, 6-dichloro-8-isopropyl-9-methyl-9H-purine compounds (structural formula is shown in formula 17 below):
Figure BDA0003927773300000232
the linear tertiary alcohol was 3-methyl-2-phenylbutan-2-ol and the capture reagent was 2, 6-dichloro-9-methyl-9H-purine but the procedure was otherwise the same as in example 11, giving a yield of 76%.
Correlation characterization analysis, the result of which is 1 H NMR(500MHz,Chloroform-d)δ3.83(s,3H),3.25(p,J＝6.9Hz,1H),1.47(d,J＝6.9Hz,6H). 13 C NMR(126MHz,Chloroform-d)δ163.96,154.84,151.76,149.61,130.10,29.29,27.37,20.61.HRMS(ESI-TOF)calculated for C 9 H 10 Cl 2 N 4 (M+H + ) 245.0355, found 245.0356. This result further confirms the molecular structure of the product as described above for molecular structure 17.
Example 18
A method for preparing a 4, 4-dimethyl-2-phenylpentanoic acid methyl ester compound (structural formula is shown as formula 18 below):
Figure BDA0003927773300000241
the photocatalyst Mes-Acr-PhBF is added 4 (0.01mmol, 4.6 mg) and the capture reagent methyl 2-phenylacrylate (0.4 mmol) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Anhydrous acetonitrile (1 mL) was added followed by the linear tertiary alcohol 3, 3-dimethyl-2-phenylbutan-2-ol (0.2 mmol). The reaction vessel was degassed, backfilled with argon and then placed in a SynLED4x4 photoreactor (SynLED discover (tm) 450 nm). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 73% yield.
Correlation characterization analysis, the result of which is 1 H NMR(400MHz,Chloroform-d)δ7.40–7.29(m,4H),7.29–7.24(m,1H),3.69(dd,J＝9.2,3.8Hz,1H),3.67(s,3H),2.34(dd,J＝14.0,9.3Hz,1H),1.61(dd,J＝14.0,3.8Hz,1H),0.93(s,9H). 13 C NMR(101MHz,Chloroform-d)δ175.25,140.91,128.62,127.78,127.02,52.04,48.07,47.41,31.00,29.38.HRMS(ESI-TOF)calculated for C 14 H 20 O 2 (M+H + ) 221.1536, found 221.1536 this result further confirms the molecular structure of the product as in molecular structure 18 above.
Example 19
A method for preparing a (3, 3-dimethylbutane-1, 1-methylsulfonyl) benzene compound (formula 19 below):
Figure BDA0003927773300000242
the photocatalyst Mes-Acr-PhBF is added 4 (0.01mmol, 4.6 mg) and the capture reagent 1, 1-bis (benzenesulfonyl) ethylene (0.4 mmol) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Anhydrous acetonitrile (1 mL) was added followed by the linear tertiary alcohol 3, 3-dimethyl-2-phenylbutan-2-ol (0.2 mmol). The reaction vessel was degassed, backfilled with argon and then placed in a SynLED4x4 photoreactor (SynLED discover (tm) 450 nm). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 78% yield.
Correlation characterization analysis, the result of which is 1 H NMR(400MHz,Chloroform-d)δ8.07–7.86(m,4H),7.76–7.65(m,2H),7.59(dd,J＝8.4,7.2Hz,4H),4.44(t,J＝4.0Hz,1H),2.22(d,J＝4.1Hz,2H),0.91(s,9H). 13 C NMR(101MHz,Chloroform-d)δ138.19,134.50,129.91,129.06,81.73,36.61,31.21,29.22.HRMS(ESI-TOF)calculated for C 18 H 22 O 4 S 2 (M-H + ) 365.0887, found 365.0886, the results further confirmed the molecular structure of the product as in molecular structure 19 above.
Example 20
A method for preparing 2- (3, 3-dimethylbutyl) pyridine compound (formula 20 below):
Figure BDA0003927773300000251
the photocatalyst Mes-Acr-PhBF is added 4 (0.01mmol, 4.6 mg) and the capture reagent 2-alkenylpyridine (0.4 mmol) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Anhydrous acetonitrile (1 mL) was added, followed by the linear tertiary alcohol 3, 3-dimethyl-2-phenylbutan-2-ol (0.2 mmol), and finally trifluoroacetic acid (0.4 mmol). The reaction vessel was degassed, backfilled with argon and then placed in a SynLED4x4 photoreactor (SynLED discover (tm) 450 nm). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 77% yield.
Correlation characterization analysis, the result is 1 H NMR(500MHz,Chloroform-d)δ8.58–8.38(m,1H),7.57(td,J＝7.6,1.9Hz,1H),7.15(dd,J＝8.0,1.1Hz,1H),7.08(ddd,J＝7.4,4.9,1.1Hz,1H),2.84–2.69(m,2H),1.67–1.54(m,2H),0.97(s,9H). 13 C NMR(126MHz,Chloroform-d)δ163.19,149.20,136.32,122.62,120.80,44.36,33.94,30.55,29.37.HRMS(ESI-TOF)calculated for C 11 H 17 N(M+H + ) 164.1434, found.
Example 21
A method for producing an (R) - (2- (tert-butyl) -6-methoxyquinolin-4-yl) ((1S, 2S,4S, 5R) -5-vinylquinolin-2-yl) methanol compound (structural formula shown in the following formula 21):
Figure BDA0003927773300000261
the linear tertiary alcohol is 3, 3-dimethyl-2-phenylbutane-2-ol, and the capture reagent is quinine; otherwise, the same procedure as in example 11 was followed, giving a yield of 60%.
Correlation characterization analysis, the result is 1 H NMR(400MHz,Chloroform-d)δ7.79(s,1H),7.66(d,J＝9.2Hz,1H),6.87(dd,J＝9.2,2.6Hz,1H),6.79(d,J＝2.7Hz,1H),6.26(s,1H),5.86(s,1H),5.56(ddd,J＝17.2,10.3,6.9Hz,1H),5.07–4.86(m,2H),4.43(s,1H),3.55(s,3H),3.37(dd,J＝13.5,10.6Hz,1H),3.26(t,J＝9.0Hz,1H),3.05(td,J＝11.7,5.1Hz,1H),2.95(ddd,J＝13.5,5.5,2.5Hz,1H),2.62(s,1H),2.30–2.15(m,1H),2.11(dd,J＝13.6,7.5Hz,1H),2.04(p,J＝3.2Hz,1H),1.87–1.72(m,1H),1.48(s,9H),1.37–1.28(m,1H). 13 C NMR(101MHz,Chloroform-d)δ165.69,157.27,143.75,143.07,137.92,131.23,123.28,121.29,116.85,115.57,99.18,66.91,60.15,56.60,55.07,43.93,37.82,37.65,30.23,27.21,24.74,18.43.HRMS(ESI-TOF)calculated for C 24 H 32 N 2 O 2 (M+H + ) 381.2537, found 381.2537. The results further confirm the molecular structure of the product as in the above molecular structure 21.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (5)

1. A photo-oxidation-reduction catalysis method, characterized by comprising the steps of:
providing a linear tertiary alcohol compound and a radical trapping reagent;
carrying out catalytic reaction on the linear tertiary alcohol compound and the free radical capture reagent under the conditions of a photocatalyst and blue light;
the linear tertiary alcohol compound comprises
Figure FDA0003927773290000011
Wherein n = an integer of 0 to 4, R 1 、R 2 And R 3 Are each independently selected from C 1 -C 20 Alkyl radical, C 1 -C 20 Heteroalkyl group, C 3 -C 20 Cycloalkyl radical, C 3 -C 20 Heterocycloalkyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 20 Heteroalkenyl, C 3 -C 20 Cycloalkenyl radical, C 3 -C 20 Heterocyclic ringsAlkenyl radical, C 2 -C 20 Alkynyl, C 2 -C 20 Heteroalkynyl, C 3 -C 20 Cycloalkynyl group, C 3 -C 20 Heterocycloalkynyl, C 1 -C 20 Alkoxy radical, C 6 -C 14 Aryl, substituted (C) 6 -C 14 ) Aryl radical, C 4 -C 14 Heteroaryl, substituted (C) 4 -C 14 ) Heteroaryl group, C 6 -C 14 Aryloxy radical, C 4 -C 14 Heteroaryloxy radical, C 6 -C 14 Aryl radical (C) 1 -C 20 ) Alkyl radical, C 4 -C 14 Heteroaryl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkenyl (C) 1 -C 20 ) Alkyl radical, C 2 -C 20 Alkynyl (C) 1 -C 20 ) Alkyl, cyano (C) 1 -C 20 ) Alkyl radical, C 1 -C 20 Alkyloxycarbonyl (C) 1 -C 20 ) Alkyl radical, C 3 -C 20 Any one of alkyl silicon base, halogen, trifluoromethoxy, sulfonamide and hydrogen atom; and R is 2 And R 3 Is not a hydrogen atom; said substituted (C) 6 -C 14 ) Aryl and said substituted (C) 4 -C 14 ) The substituents in the heteroaryl group are independently selected from halogen atom and C 1 -C 5 Alkyl radical, C 1 -C 5 At least one of alkoxy, nitro and acyl;
the free radical capture reagent is selected from heterocyclic compounds selected from at least one of quinoline, quinoline derivatives, pyridine derivatives, thiazole derivatives, benzothiazole derivatives, pyrazine derivatives, pyrimidine derivatives, purine and purine derivatives;
the photocatalyst is selected from acridine salt catalysts;
the catalytic reaction is also added with a Bronsted acid reagent, an oxidant and an acetonitrile solvent.
2. The photo-redox catalytic process of claim 1, wherein R is 1 、R 2 And R 3 Are each independently selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Heteroalkyl group, C 3 -C 10 Cycloalkyl, C 3 -C 10 Heterocycloalkyl, C 2 -C 10 Alkenyl radical, C 2 -C 10 Heteroalkenyl, C 3 -C 10 Cycloalkenyl radical, C 3 -C 10 Heterocycloalkenyl, C 2 -C 10 Alkynyl, C 2 -C 10 Heteroalkynyl, C 3 -C 10 Cycloalkynyl group, C 3 -C 10 Heterocycloalkynyl, C 1 -C 10 Alkoxy radical, C 6 -C 14 Aryl, substituted (C) 6 -C 14 ) Aryl radical, C 4 -C 14 Heteroaryl, substituted (C) 4 -C 14 ) Heteroaryl group, C 6 -C 14 Aryloxy radical, C 4 -C 14 Heteroaryloxy radical, C 6 -C 14 Aryl radical (C) 1 -C 10 ) Alkyl radical, C 4 -C 14 Heteroaryl (C) 1 -C 10 ) Alkyl radical, C 2 -C 10 Alkenyl (C) 1 -C 10 ) Alkyl radical, C 2 -C 10 Alkynyl (C) 1 -C 10 ) Alkyl, cyano (C) 1 -C 10 ) Alkyl radical, C 1 -C 10 Alkyloxycarbonyl (C) 1 -C 10 ) Alkyl and C 3 -C 10 Any one of alkylsilyl groups.
3. The photoredox catalytic process according to any of claims 1-2 wherein the photocatalyst is an acridine salt catalyst as shown below;
Figure FDA0003927773290000021
wherein X is a tetrafluoroborate anion, a hexafluorophosphate anion or a perchlorate anion; r 4 、R 5 And R 6 Are each independently selected from C 1 -C 20 Alkyl radical, C 1 -C 20 Heteroalkyl group, C 3 -C 20 Cycloalkyl radical, C 3 -C 20 Heterocycloalkyl, C 2 -C 20 Alkenyl radical, C 2 -C 20 Heteroalkenyl, C 3 -C 20 Cycloalkenyl radical, C 3 -C 20 Heterocycloalkenyl, C 2 -C 20 Alkynyl, C 2 -C 20 Heteroalkynyl, C 3 -C 20 Cycloalkynyl group, C 3 -C 20 Heterocycloalkynyl, C 1 -C 20 Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C) 1 -C 20 ) Alkyl, heteroaryl (C) 1 -C 20 ) Alkyl, (C) 2 -C 20 ) Alkenyl (C) 1 -C 20 ) Alkyl, (C) 2 -C 20 ) Alkynyl (C) 1 -C 20 ) Alkyl and cyano (C) 1 -C 20 ) Any one of alkyl groups.
4. The photoredox catalytic process according to any of claims 1-2, wherein the bronsted acid reagent is selected from at least one of acetic acid, fluoroacetic acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid; and/or the presence of a gas in the gas,
the oxidant is at least one selected from a high-valence iodine compound, a peroxy compound, a quinone compound, persulfate, potassium permanganate, oxygen and N-fluorobenzenesulfonylimide.
5. The photoredox catalysis method of any of claims 1-2, wherein a molar ratio of the photocatalyst, the oxidant, and the Bronsted acid reagent is (0.1-20): (0.2-40).
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