CN115710199B - Photooxidation reduction catalytic process - Google Patents

Photooxidation reduction catalytic process Download PDF

Info

Publication number
CN115710199B
CN115710199B CN202211378442.0A CN202211378442A CN115710199B CN 115710199 B CN115710199 B CN 115710199B CN 202211378442 A CN202211378442 A CN 202211378442A CN 115710199 B CN115710199 B CN 115710199B
Authority
CN
China
Prior art keywords
alkyl
tertiary alcohol
free radical
aryl
linear tertiary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211378442.0A
Other languages
Chinese (zh)
Other versions
CN115710199A (en
Inventor
黄湧
陈杰安
廖柯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Bay Laboratory Pingshan Biomedical R & D And Transformation Center
Original Assignee
Shenzhen Bay Laboratory Pingshan Biomedical R & D And Transformation Center
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Bay Laboratory Pingshan Biomedical R & D And Transformation Center filed Critical Shenzhen Bay Laboratory Pingshan Biomedical R & D And Transformation Center
Priority to CN202211378442.0A priority Critical patent/CN115710199B/en
Publication of CN115710199A publication Critical patent/CN115710199A/en
Application granted granted Critical
Publication of CN115710199B publication Critical patent/CN115710199B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C07B61/02—Generation of organic free radicals; Organic free radicals per se
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
    • C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
    • C07D453/04—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems
    • C07D473/40—Heterocyclic compounds containing purine ring systems with halogen atoms or perhalogeno-alkyl radicals directly attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

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

Description

Photooxidation reduction catalytic process
The application is a divisional application with the application number 202110588659.3 and the application date 2021-05-28, and the application name of photo-redox catalytic method.
Technical Field
The application belongs to the technical field of synthetic chemistry, and particularly relates to a photo-oxidation reduction catalytic method.
Background
In recent years, with the understanding of photocatalytic mechanism and development of photo-redox catalysts, visible light-promoted photo-redox catalysis (photoredox catalysis) has been rapidly developed, and remarkable achievement has been achieved, and modern free radical chemistry has been thoroughly changed.
Through research, alkyl radicals play an indispensable role in the development of novel synthesis methods under photo/electrochemical catalysis. In general, alkyl radical precursors undergo single electron transfer with the aid of a photo-redox catalyst to generate transient alkyl radicals that can participate in various bond formation processes in a chemical and stereoselective manner, and a number of alkyl radical precursors have been developed that have a built-in redox group that reduces the energy gap between the substrate and the excited state of the photosensitizer. Despite the remarkable progress of the above-described studies, the use of common, environmentally friendly chemical raw materials to generate alkyl radicals in a precisely controlled manner has received little attention. The direct generation of alkyl radicals from simple, unactivated alcohols remains a primary challenge in photo-redox catalysis due to the high oxidation potential of alcohols.
Disclosure of Invention
The application aims to provide a photo-redox catalytic method, which aims to solve the technical problem of how to use linear tertiary alcohol to expand designable compounds at low cost.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
A photo-redox catalytic method comprising the steps of:
providing a linear tertiary alcohol compound and a free radical trapping agent;
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;
The linear tertiary alcohol compound comprises
Wherein n=an integer of 0 to 4, R 1、R2 and R 3 are each independently selected from C 1-C20 alkyl, C 1-C20 heteroalkyl, C 3-C20 cycloalkyl, C 3-C20 heterocycloalkyl, C 2-C20 alkenyl, C 2-C20 heteroalkenyl, C 3-C20 cycloalkenyl, C 3-C20 heterocycloalkenyl, C 2-C20 alkynyl, C 2-C20 heteroalkynyl, C 3-C20 cycloalkynyl, C 3-C20 heterocycloalkynyl, c 1-C20 alkoxy, C 6-C14 aryl, substituted (C 6-C14) aryl, C 4-C14 heteroaryl, substituted (C 4-C14) heteroaryl, C 6-C14 aryloxy, C 4-C14 heteroaryloxy, C 6-C14 aryl (C 1-C20) alkyl, C 4-C14 heteroaryl (C 1-C20) alkyl, C 2-C20 alkenyl (C 1-C20) alkyl, C 2-C20 alkynyl (C 1-C20) alkyl, cyano (C 1-C20) alkyl, Any one of C 1-C20 alkyloxycarbonyl (C 1-C20) alkyl, C 3-C20 alkylsilyl, halogen, trifluoromethoxy, sulfonamide, and hydrogen atom; and R 2 and R 3 are not hydrogen atoms; The substituents in the substituted (C 6-C14) aryl and the substituted (C 4-C14) heteroaryl are each independently selected from the group consisting of halogen atoms, C 1-C5 alkyl groups, C 1-C5 alkoxy groups, At least one of a nitro group and an acyl group;
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 type catalysts;
The photocatalytic reaction is also added with a Bronsted acid reagent, an oxidant and an acetonitrile solvent.
The photooxidation reduction catalysis method provided by the application is a new method for expanding alkyl free radical chemistry by alcohol, under the condition of a photocatalyst, linear tertiary alcohol generates alkyl free radicals by single-electron oxidation induced carbon-carbon bond fracture, and then the alkyl free radicals are captured by a free 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 product, and can be widely applied to the fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicine research.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship. "at least one" means one or more, and "plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of 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 functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in 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 weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be a mass unit which is known in the chemical industry field such as mu g, mg, g, kg.
The compounds and derivatives thereof referred to in the examples of the present application are named according to the IUPAC (International Union of pure and applied chemistry) or CAS (chemical abstract service Co., ltd., columbus, ohio) naming system. Thus, the compound groups specifically referred to in the examples of the present application are described and illustrated as follows:
With respect to "hydrocarbon groups", the minimum and maximum values of the carbon atom content in the hydrocarbon groups are indicated by a prefix, for example, the prefix (Ca-Cb) alkyl indicates any alkyl group containing from "a" to "b" carbon atoms. Thus, for example, (C 1-C6) alkyl refers to alkyl groups containing one to six carbon atoms.
"Alkoxy" refers to a straight or branched saturated aliphatic chain bonded to an oxygen atom and includes, but is not limited to, groups such as methoxy, ethoxy, propoxy, butoxy, isobutoxy, t-butoxy, and the like. (C a-Cb) alkoxy means any straight or branched, monovalent, saturated aliphatic chain having an alkyl group of "a" to "b" carbon atoms bonded to an oxygen atom.
"Alkyl" refers to a straight or branched saturated aliphatic chain including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and the like.
"Heteroalkyl" refers to a straight or branched, saturated aliphatic chain containing at least one heteroatom attached, such as, but not limited to, methylaminoethyl, methyloxypropyl, or other similar groups.
"Alkenyl" refers to straight or branched chain hydrocarbons with one or more double bonds, including but not limited to, e.g., ethenyl, propenyl, and the like.
"Heteroalkenyl" refers to a straight or branched hydrocarbon containing at least one heteroatom linkage bearing one or more double bonds, including but not limited to, e.g., vinylaminoethyl or other similar groups.
"Alkynyl" refers to a straight or branched hydrocarbon bearing one or more triple bonds, including but not limited to, e.g., ethynyl, propynyl, and the like.
"Heteroalkynyl" refers to a straight or branched hydrocarbon containing at least one heteroatom linkage, bearing one or more triple bonds.
"Aryl" refers to a cyclic aromatic hydrocarbon, which may be a single or multiple ring or fused ring aromatic hydrocarbon, including, but not limited to, groups such as phenyl, naphthyl, anthryl, phenanthryl, and the like.
"Heteroaryl" means that one or more carbon atoms in a monocyclic or polycyclic or fused ring aromatic hydrocarbon have been replaced by heteroatoms such as nitrogen, oxygen or sulfur. If the heteroaryl group contains more than one heteroatom, these heteroatoms may be the same or may be different. Heteroaryl groups include, but are not limited to, 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, pyridin [3,4-b ] indolyl, pyridinyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolinyl, 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, for example, 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. Heterocyclylalkyl groups include, but are not limited to, for example, azabicycloheptyl, azetidinyl, indolinyl, morpholinyl, pyrazinyl, piperidinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroindazolyl, tetrahydroindolyl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydroquinoxalinyl, tetrahydrothiopyranyl, thiazolidinyl, thiomorpholinyl, thioxanthyl, thiooxalkyl, 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 vinyl, cyclopropenyl, or other similar groups.
"Heterocycloalkenyl" refers to an unsaturated monocyclic or polycyclic alkenyl group having one or more double bonds in which at least one carbon atom is replaced with 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 an unsaturated, mono-or polycyclic alkynyl group bearing one or more triple bonds, possibly fused to an aromatic hydrocarbon group, including but not limited to cycloalkynyl, cyclopropynyl, or other like groups.
"Heterocycloalkynyl" refers to an unsaturated monocyclic or polycyclic alkynyl group having one or more triple bonds in which at least one carbon atom is replaced with a heteroatom such as nitrogen, oxygen or sulfur, possibly fused to an aromatic hydrocarbon group. If the heterocycloalkynyl contains more than one heteroatom, these heteroatoms may be the same or may be different.
The hetero atom may be an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
"Tertiary alcohol" refers to a tertiary alcohol, i.e., an alcohol having three non-hydrogen substituent groups at the position of the hydroxyl group. "Linear tertiary alcohol" means that the carbon at the position of the hydroxyl group of the tertiary alcohol is linear or straight (linear), and "cyclic tertiary alcohol" corresponding to this means that the carbon at the position of the hydroxyl group of the tertiary alcohol is cyclic.
The embodiment of the application provides a photo-redox catalytic method, which comprises the following steps:
S01: providing a linear tertiary alcohol compound and a free radical trapping agent;
S02: the linear tertiary alcohol compound and the free radical capture reagent are subjected to catalytic reaction under the condition of a photocatalyst.
The photooxidation reduction catalysis method provided by the application is a new method for expanding alkyl free radical chemistry by alcohol, under the condition of a photocatalyst, linear tertiary alcohol generates alkyl free radicals by single-electron oxidation induced carbon-carbon bond fracture, and then the alkyl free radicals are captured by a free radical capture reagent to react to obtain various products; the photooxidation reduction catalysis method obviously reduces the production cost for preparing the captured product, greatly expands the designability and application prospect of the product, and the reactant raw materials provided by the embodiment of the application are very easy to obtain, and the reactant before reaction does not need to be subjected to additional modification and can be directly used for preparation and production, so that the operation steps are simplified, and the reaction route is shortened; 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,
The linear tertiary alcohol compound comprises
Wherein n=an integer of 0 to 4 (e.g., n may be 0, 1,2, 3 or 4), R 1、R2 and R 3 are each independently selected from C 1-C20 alkyl, C 1-C20 heteroalkyl, C 3-C20 cycloalkyl, C 3-C20 heterocycloalkyl, C 2-C20 alkenyl, C 2-C20 heteroalkenyl, C 3-C20 cycloalkenyl, C 3-C20 heterocycloalkenyl, C 2-C20 alkynyl, C 2-C20 heteroalkynyl, C 3-C20 cycloalkynyl, C 3-C20 heterocycloalkynyl, C 1-C20 alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C 1-C20) alkyl, heteroaryl (C 1-C20) alkyl, C 2-C20 alkenyl (C 1-C20) alkyl, C 2-C20 alkynyl (C 1-C20) alkyl, cyano (C 1-C20) alkyl, C 1-C20 alkyloxycarbonyl (C 1-C20) alkyl, Any one of C 3-C20 alkyl silicon group, halogen, trifluoromethoxy group, sulfonamide group and hydrogen atom; And R 2 and R 2 are not hydrogen atoms.
R 1、R2 and R 3 are identical or different and are selected from C 1-C20 alkyl, C 1-C20 heteroalkyl, C 3-C20 cycloalkyl, C 3-C20 heterocycloalkyl, C 2-C20 alkenyl, C 2-C20 heteroalkenyl, C 3-C20 cycloalkenyl, C 3-C20 heterocycloalkenyl, C 2-C20 alkynyl, C 2-C20 heteroalkynyl, C 3-C20 cycloalkynyl, C 3-C20 heterocycloalkynyl, C 1-C20 alkoxy, Aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C 1-C20) alkyl, heteroaryl (C 1-C20) alkyl, C 2-C20 alkenyl (C 1-C20) alkyl, C 2-C20 alkynyl (C 1-C20) alkyl, cyano (C 1-C20) alkyl, C 1-C20 alkyloxycarbonyl (C 1-C20) alkyl, Any one of C 3-C20 alkyl silicon group, halogen (such as fluorine, chlorine, bromine and iodine), trifluoro methoxy, sulfonamide and hydrogen atom, which means that R 1、R2 and R 3 are respectively and independently selected from the above groups, and can be the same or different; And R 2 and R 2 are not hydrogen atoms.
When R 1、R2 or R 3 is selected from C 1-C20 alkyl, in one embodiment, the (C 1-C20) alkyl can be (C 1-C10) alkyl, (C 1-C5) alkyl, (C 1-C4) alkyl, (C 1-C3) alkyl, (C 1-C2) alkyl, and the like. In certain embodiments, (C 1-C20) alkyl may be methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, and the like.
When R 1、R2 or R 3 is selected from (C 1-C20) heteroalkyl, in one embodiment, the (C 1-C20) heteroalkyl may be (C 1-C10) heteroalkyl, (C 2-C5) heteroalkyl, (C 3-C4) heteroalkyl, and the like. In certain embodiments, the heteroatom may be an atom, a nitrogen atom, a sulfur atom, or the like.
When R 1、R2 or R 3 is selected from (C 3-C20) cycloalkyl, in one embodiment, the (C 3-C20) cycloalkyl can be (C 3-C10) cycloalkyl, (C 3-C5) cycloalkyl, (C 3-C4) cycloalkyl, and the like. In certain embodiments, (C 3-C20) cycloalkyl may be cyclopropyl, cyclobutyl, cyclopentyl, and the like.
When R 1、R2 or R 3 is selected from (C 3-C20) heterocycloalkyl, in one embodiment, the (C 3-C20) heterocycloalkyl may be (C 3-C10) heterocycloalkyl, (C 3-C10) heterocycloalkyl, (C 3-C5) heterocycloalkyl, (C 3-C4) heterocycloalkyl, and the like. In certain embodiments, the heteroatom may be an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
When R 1、R2 or R 3 is selected from (C 2-C20) alkenyl, in one embodiment, the (C 2-C20) alkenyl can be (C 3-C10) alkenyl, (C 3-C5) alkenyl, (C 3-C4) alkenyl, (C 2-C3) alkenyl, and the like. In certain embodiments, (C 2-C20) alkenyl may be ethenyl, propenyl, butenyl, pentenyl, and the like.
When R 1、R2 or R 3 is selected from (C 2-C20) heteroalkenyl, in one embodiment, the (C 2-C20) heteroalkenyl may be (C 2-C10) heteroalkenyl, (C 3-C10) heteroalkenyl, (C 3-C5) heteroalkenyl, and the like. In certain embodiments, the heteroatom may be halogen, nitrogen atom, sulfur atom, or the like.
When R 1、R2 or R 3 is selected from (C 3-C20) cycloalkenyl, in one embodiment, the (C 3-C20) cycloalkenyl may be (C 3-C10) cycloalkenyl, (C 3-C5) cycloalkenyl, (C 3-C4) cycloalkenyl, and the like. In certain embodiments, (C 3-C20) cycloalkenyl may be cyclopropenyl, cyclobutenyl, cyclopentenyl, and the like.
When R 1、R2 or R 3 is selected from (C 3-C20) heterocycloalkenyl, in one embodiment, the (C 3-C20) heterocycloalkenyl can be (C 3-C10) heterocycloalkenyl, (C 3-C5) heterocycloalkenyl, (C 3-C4) heterocycloalkenyl, and the like. In certain embodiments, the heteroatom may be halogen, nitrogen atom, sulfur atom, or the like.
When R 1、R2 or R 3 is selected from (C 2-C20) alkynyl, in one embodiment, the (C 2-C20) alkynyl may be (C 2-C10) alkynyl, (C 3-C10) alkynyl, (C 3-C5) alkynyl, (C 3-C4) alkynyl, (C 2-C3) alkynyl, and the like. In certain embodiments, (C 2-C20) alkynyl may be ethynyl, propynyl, butynyl, pentynyl, and the like.
When R 1、R2 or R 3 is selected from (C 2-C20) heteroalkynyl, (C 2-C20) heteroalkynyl, (C 3-C10) heteroalkynyl, (C 3-C5) heteroalkynyl, (C 3-C4) heteroalkynyl, and the like, in one embodiment, the (C 2-C20) heteroalkynyl may be (C 2-C10) heteroalkynyl, (C 3-C10) heteroalkynyl, and the like. In certain embodiments, the heteroatom may be halogen, nitrogen atom, sulfur atom, or the like.
When R 1、R2 or R 3 is selected from (C 3-C20) cycloalkynyl, in one embodiment, the (C 3-C20) cycloalkynyl can be (C 3-C10) cycloalkynyl, (C 3-C5) cycloalkynyl, (C 3-C4) cycloalkynyl, and the like. In certain embodiments, (C 2-C20) cycloalkynyl may be cyclopropynyl, cyclobutynyl, cyclopentynyl, and the like.
When R 1、R2 or R 3 is selected from (C 3-C20) heterocycloalkynyl, in one embodiment, the (C 3-C20) heterocycloalkynyl can be (C 3-C10) heterocycloalkynyl, (C 3-C5) heterocycloalkynyl, (C 3-C4) heterocycloalkynyl, and the like. In certain embodiments, the heteroatom may be halogen, nitrogen atom, sulfur atom, or the like.
When R 1、R2 or R 3 is selected from (C 1-C20) alkoxy, in one embodiment, the (C 1-C20) alkoxy may be (C 1-C10) alkoxy, (C 1-C8) alkoxy, (C 1-C6) alkoxy, (C 1-C4) alkoxy, (C 1-C3) alkoxy, (C 1-C2) alkoxy. In certain embodiments, the (C 1-C20) alkoxy group may be, but is not limited to, methyl oxy, ethyl oxy, propyl oxy, and the like.
When R 1、R2 or R 3 is selected from aryl, the aryl may be, but is not limited to, monocyclic aryl, polycyclic aryl, fused ring aryl. In one embodiment, the aryl is a monocyclic aryl. In certain embodiments, the aryl group may be a C 4-C14 aryl group, such as phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and the like.
When R 1、R2 or R 3 is selected from substituted aryl groups, the substituted aryl groups may be, but are not limited to, ortho, meta, para single or multiple substituted phenyl groups. Substituents include, but are not limited to, alkyl, substituted alkyl, aryl, substituted aryl, acyl, halogen, alkoxy, nitro. Wherein, when the substituent is an alkyl group, the alkyl group is for example 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, a methyloxy group, an ethyloxy group, a propyloxy group. In one embodiment, the substituted aryl may be a substituted (C 4-C14) aryl, such as may be cyano (C 1-C10) alkyl (C 4-C8) aryl, substituted (C 4-C8) aryl.
When R 1、R2 or R 3 is selected from heteroaryl, in one embodiment, the heteroaryl may be (C 4-C14) heteroaryl, such as thienyl, thiazolyl, pyrrolyl, pyrazinyl, pyridyl, benzothiophene, and the like.
When R 1、R2 or R 3 is selected from substituted heteroaryl, in one embodiment, the substituted heteroaryl may be a substituted (C 4-C14) heteroaryl, such as an alkoxy substituted furan, (C 3-C8) heteroaryl substituted furan, a fatty chain substituted thiophene, and the like.
When R 1、R2 or R 3 is selected from aryloxy, in one embodiment, the aryloxy may be a C 4-C14 aryloxy such as phenoxy, naphthoxy, anthracenoxy, phenanthryloxy, and the like.
When R 1、R2 or R 3 is selected from heteroaryloxy, in one embodiment, the heteroaryloxy may be C 4-C14 heteroaryloxy.
When R 1、R2 or R 3 is selected from aryl (C 1-C20) alkyl, in one embodiment, the aryl (C 1-C20) alkyl can be C 4-C14 aryl (C 1-C10) alkyl, such as phenyl (C 1-C10) alkyl, phenyl (C 1-C5) alkyl, phenyl (C 1-C4) alkyl, phenyl (C 1-C3) alkyl, phenyl (C 1-C2) alkyl, and the like. In certain embodiments, aryl (C 1-C20) alkyl may be phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylisobutyl, phenylpentyl, phenylisopentyl, phenylneopentyl, and the like.
When R 1、R2 or R 3 is selected from heteroaryl (C 1-C20) alkyl, in one embodiment, the heteroaryl (C 1-C20) alkyl can be C 4-C14 heteroaryl (C 1-C10) alkyl, such as heteroaryl (C 1-C10) alkyl, heteroaryl (C 1-C5) alkyl, heteroaryl (C 1-C4) alkyl, heteroaryl (C 1-C3) alkyl, heteroaryl (C 1-C2) alkyl, and the like.
When R 1、R2 or R 3 is selected from (C 2-C20) alkenyl (C 1-C20) alkyl, in one embodiment, the (C 2-C20) alkenyl (C 1-C20) alkyl may be (C 2-C10) alkenyl (C 1-C10) alkyl, (C 2-C5) alkenyl (C 1-C3) alkyl, and the like.
When R 1、R2 or R 3 is selected from (C 2-C20) alkynyl (C 1-C20) alkyl, in one embodiment, the (C 2-C20) alkynyl (C 1-C20) alkyl may be (C 2-C10) alkynyl (C 1-C10) alkyl, (C 2-C5) alkynyl (C 1-C3) alkyl, and the like.
When R 1、R2 or R 3 is selected from cyano (C 1-C20) alkyl, in one embodiment, the cyano (C 1-C20) alkyl can be cyano (C 1-C10) alkyl, cyano (C 1-C5) alkyl, cyano (C 1-C4) alkyl, cyano (C 1-C3) alkyl, cyano (C 1-C2) alkyl, and the like. In certain embodiments, the cyano (C 1-C20) alkyl group can be cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, and the like.
When R 1、R2 or R 3 is selected from C 3-C20 alkylsilyl, in one embodiment, the C 3-C20 alkylsilyl may be C 3-C18 alkylsilyl, C 3-C10 alkylsilyl, C 3-C5 alkylsilyl, and the like.
When R 1、R2 or R 3 is selected from C 1-C20 alkyloxycarbonyl (C 1-C20) alkyl, in one embodiment, the C 1-C20 alkyloxycarbonyl (C 1-C20) alkyl can be (C 1-C10) alkyloxycarbonyl (C 1-C10) alkyl, (C 1-C5) alkyloxycarbonyl (C 1-C5) alkyl, (C 1-C4) alkyloxycarbonyl (C 1-C4) alkyl, and the like.
The radical trapping agent may be at least one selected from the group consisting of electron-deficient alkenyl group-containing compounds, heterocyclic compounds, and thiotrifluoromethyl radical precursors, and for example, the present application is selected from the group consisting of heterocyclic compounds. The unactivated linear tertiary alcohols of the present application are oxidized by a photocatalyst, and the resulting alkoxy groups selectively undergo β -scission to deliver alkyl radicals that can be accepted by a variety of nucleophiles, thereby being captured by the radical capture reagents described above for addition or substitution to yield the product.
Specifically, the electron-deficient alkenyl-containing compound of the radical trapping agent is selected from at least one of benzyl malononitrile, 1-bis (phenylsulfonyl) ethylene, methyl 2-phenylacrylate and 2-vinylpyridine; the above electron-deficient alkenyl group-containing compound is catalytically reacted with a linear tertiary alcohol compound to obtain an addition product of a primary alkyl radical, a secondary alkyl radical or a tertiary alkyl radical with the above-mentioned electron-deficient alkenyl group-containing compound such as benzyl malononitrile, 1-bis (phenylsulfonyl) ethylene, methyl 2-phenylacrylate, 2-vinylpyridine and the like.
Or the heterocyclic compound of the radical trapping agent is a heterocyclic compound containing a nitrogen atom, such as at least one selected from the group consisting of quinoline, a quinoline derivative, pyridine, a pyridine derivative, thiazole, a thiazole derivative, benzothiazole, a benzothiazole derivative, pyrazine, a pyrazine derivative, pyrimidine, a pyrimidine derivative, purine and a purine derivative; the heterocyclic compound 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 which reacts with the heterocyclic compound to generate a monosubstituted alkyl substituted product. Further, the quinoline derivatives may be quinoline substituted with an alkyl group or other groups, such as 2-methylquinoline, quinine, etc.; the pyridine derivative may be an alkyl group or other group-substituted pyridine such as 2, 6-lutidine and the like; the thiazole derivative can be thiazole substituted by alkyl or other groups, such as 5-methylthiazole-4-carboxylic acid ethyl ester and the like; the pyrazine derivatives can be alkyl or other groups substituted pyrazines, such as 2,3, 5-trimethylpyrazine and the like; the pyrimidine derivative may be an alkyl or other group-substituted pyrimidine such as 4, 6-dimethylpyrimidine, etc.; the above purine derivatives may be alkyl or other group substituted purines such as 2, 6-dichloro-9-methyl-9H-purine and the like.
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 linear tertiary alcohol compound are subjected to catalytic reaction to obtain the corresponding sulfur trifluoromethyl substituted alkyl product.
The linear tertiary alcohol compound acts as a nucleophile and is capable of attacking at least one of the electron deficient alkenyl containing compound, the heterocyclic compound and the thiotrifluoromethyl radical precursor, such that the two reactants react. Therefore, the atomic utilization rate of the reactant is effectively improved, the limitation of the substrate is widened, the target product precursor with high enantioselectivity and extremely wide range is efficiently and greenly prepared, and the product with potential application value is obtained through simple reduction reaction.
In one embodiment, the photocatalyst is an acridine salt catalyst as shown below;
Wherein X is tetrafluoroboric acid anion, hexafluorophosphoric acid anion or perchloric acid anion; R 4、R5 and R 6 are each independently selected from the group consisting of C 1-C20 alkyl, C 1-C20 heteroalkyl, C 3-C20 cycloalkyl, C 3-C20 heterocycloalkyl, C 2-C20 alkenyl, C 2-C20 heteroalkenyl, C 3-C20 cycloalkenyl, C 3-C20 heterocycloalkenyl, C 2-C20 alkynyl, C 2-C20 heteroalkynyl, C 3-C20 cycloalkynyl, C 3-C20 heterocycloalkynyl, C 1-C20 alkoxy, Aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C 1-C20) alkyl, heteroaryl (C 1-C20) alkyl, (C 2-C20) alkenyl (C 1-C20) alkyl, Any one of (C 2-C20) alkynyl (C 1-C20) alkyl and cyano (C 1-C20) alkyl. the catalyst has better photo-oxidation reduction catalytic effect. In a preferred embodiment of the 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 to the above-mentioned catalytic reaction. Specifically, the two are added, and the photocatalyst, the oxidant and the Bronsted acid reagent act synergistically, so that the catalytic system has low toxicity, the atom utilization rate and the reaction efficiency are improved, and the byproducts are few; meanwhile, the reaction process is safe and controllable, and the operation in the preparation and production processes is simplified. The photocatalyst can provide better single-electron oxidation, 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 with heterocycles. Specifically, the bronsted acid reagent is at least one selected from 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 hypervalent iodine compound, a peroxy compound, a quinone compound, a persulfate, potassium permanganate, oxygen and N-fluorobenzenesulfonimide.
Under the condition that the contents of the three are in a certain range and in proportion, the reaction has higher efficient catalytic efficiency, and the target product with higher yield is obtained. Specifically, the molar ratio of the photocatalyst to the oxidant to the Bronsted acid reagent is (0.1-20): 0.2-40. Under the proportion, the reaction has high catalytic efficiency, and is favorable for improving the yield of reaction products. Preferably, the molar ratio of the photocatalyst, the oxidizing agent and the Bronsted acid reagent is (0.2-20) 2.5 (1-10), in which case the highest yield of the target product is advantageously obtained.
In one embodiment, the catalytic reaction is performed by dissolving a linear tertiary alcohol compound and a free 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 free radical capture reagent are added into acetonitrile solution containing acridine salt photocatalyst, and the mixture is reacted under blue light irradiation to obtain a product after alkyl free radical and the capture reagent are added, wherein the additive can comprise a Bronsted acid reagent and an oxidant.
The linear tertiary alcohol compound is oxidized through single electron transfer, so that carbon-carbon bond breakage is induced, and then the linear tertiary alcohol compound reacts with a free radical capture reagent; has the following advantages: the substrate range is wider by breaking the carbon-carbon bond of the linear tertiary alcohol, and the generated alkyl free radical can be captured by various free radical capture reagents. It is worth noting that quinine widely applied in asymmetry and medicines can be well modified, the reaction process is safe and controllable, and the operation in the preparation and production processes is simplified. In addition, the application 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 functionality, is more diversified in the synthesis of the drug intermediate, the application of the functional material and the metal ligand, can be widely used for the synthesis of the drug intermediate, the preparation of the chiral ligand and the functional material, can effectively reduce the economic cost of the preparation of the drug intermediate and the functional material, and provides the environmental friendliness. The cleavage method and the capture product provided by the application have high functionality, and can be widely applied to the fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicine research, such as the fields of synthesis of pharmaceutical intermediates, particularly compounds containing hetero quaternary carbon center structures, and preparation of functional materials.
The application carries out photooxidation reduction catalytic reaction by using different kinds of linear tertiary alcohol compounds and different kinds of free radical capture reagents, thereby obtaining different kinds of products. Specifically, the embodiment of the application provides the photo-redox catalytic method, which utilizes different raw materials to obtain 21 products as follows.
The compound obtained by the photocatalysis method can be used for synthesizing a drug intermediate, preparing a functional material and a metal ligand, so that the preparation method has good application prospect.
The following description is made with reference to specific embodiments.
Example 1
A preparation method of 2- (1, 2-diphenyl ethyl) malononitrile compound (structural formula is shown as the following formula 1) comprises:
The photocatalyst Mes-Acr-PhBF 4 (0.01 mmol,4.6 mg) and the capture reagent benzyl malononitrile (0.4 mmol,61.7 mg) were weighed into oven-dried 8mL vials containing magnetic star bars. 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 SynLED x4 photoreactor (SynLED discoverTM nm, 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 give the desired product in 85% yield.
The results of the correlation characterization analysis were 1H 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).13C 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 C17H14N2(M+Na+):269.1049,found:269.1049.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 1.
Example 2
A preparation method of 2- (1, 3-diphenylpropyl) malononitrile compound (structural formula is shown as the following formula 2):
the linear tertiary alcohol is 3-methyl-1-phenyl-3-amyl alcohol, and the capturing reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 1 was carried out, with a yield of 81%.
The result of the correlation characterization analysis is 1H 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).13C 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 C18H16N2(M+Na+):283.1206,found:283.1206.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 2.
Example 3
A process for producing a 2- (2- (4-isobutylphenyl) -1-phenylpropyl) malononitrile compound (structural formula 3:
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 carried out, with a yield of 84% and a dr of 1:1.
Correlation characterization analysis, the result is isomer 1:1H 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).13C 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 2:1H 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).13C 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 C22H24N2(M-H+):315.1867,found:315.1868. this result further demonstrates the product molecular structure as described above for molecular structure 3.
Example 4
A process for producing a 2- (1, 2-diphenylbutyl) malononitrile compound (structural formula 4 shown below):
The linear tertiary alcohol is 2-methyl-3-phenylpentane-2-alcohol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 1 was carried out, with a yield of 93% and a dr of 1:1.
Correlation characterization analysis, the result is isomer 1:1H 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).13C 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 2:1H 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).13C 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 C19H18N2(M-H+):273.1397,found:273.1399. this result further demonstrates the product molecular structure as described above for molecular structure 4.
Example 5
A preparation method of 2- (2-methoxy-1-phenethyl) malononitrile compound (structural formula is shown as the following formula 5):
the photocatalyst Mes-Acr-PhBF 4 (0.01 mmol,4.6 mg) and the capture reagent benzyl malononitrile (0.2 mmol,30.8 mg) were weighed into oven-dried 8mL vials containing magnetic star bars. 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 SynLED x4 photoreactor (SynLED discoverTM 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 give the desired product in 92% yield.
The results of the correlation characterization analysis were 1H 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).13C 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 C12H12N2O(M-H+):199.0877,found:199.0874.. This result further demonstrates the product molecular structure as described above for molecular structure 5.
Example 6
A process for producing a 2- (phenyl (tetrahydro-2H-pyran-4-yl) methyl) malononitrile compound (structural formula 6:
The linear tertiary alcohol is 1-phenyl-1- (tetrahydro-2H-pyran-4-yl) ethan-1-ol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was carried out, with a yield of 94%.
The results of the correlation characterization analysis were 1H 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).13C 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 C15H16N2O(M-H+):239.1190,found:239.1189.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 6.
Example 7
A preparation method of 2- (1-phenyldodecyl) malononitrile compound (structural formula is shown as formula 7 below) comprises:
The linear tertiary alcohol is 2-phenyl-tridecyl-2-alcohol, and the capturing reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was carried out, with a yield of 77%.
The results of the correlation characterization analysis were 1H 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).13C 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 C21H30N2(M-H+):309.2336,found:309.2338.. This result further demonstrates the product molecular structure as described above for molecular structure 7.
Example 8
A method for producing a 2- ((4, 4-difluorocyclohexyl) (phenyl) methyl) malononitrile compound (structural formula 8 shown below):
The linear tertiary alcohol is 1- (4, 4-difluorocyclohexyl) -1-phenylethan-1-ol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was carried out, with a yield of 76%.
The results of the correlation characterization analysis were 1H 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).13C 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).19F NMR(376MHz,Chloroform-d)δ-93.10(d,J＝237.2Hz),-103.04(d,J＝237.6Hz).HRMS(ESI-TOF)calculated for C16H16F2N2(M-H+):273.1209,found:273.1210.. This result further demonstrates the product molecular structure as described above for molecular structure 8.
Example 9
A method for preparing a 2- ((((3 r,5r,7 r) -adamantan-1-yl) (phenyl) methyl) malononitrile compound (structural formula is shown as the following formula 9):
the linear tertiary alcohol is 1- ((3 r,5r,7 r) -adamantan-1-yl) -1-phenylethan-1-ol, and the capture reagent is benzyl allyl dinitrile; otherwise, the same procedure as in example 5 was carried out, with a yield of 85%.
The results of the correlation characterization analysis were 1H 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).13C 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 C20H22N2(M-H+):289.1710,found:289.1709.. This result further demonstrates the product molecular structure as described above for molecular structure 9.
Example 10
A process for producing a 2- (2- (allyloxy) -1-phenethyl) malononitrile compound (structural formula 10:
The linear tertiary alcohol was 1- (allyloxy) -2-phenylpropan-2-ol and the trapping agent was benzyl malononitrile in 68% yield in the same manner as in example 5.
The results of the correlation characterization analysis were 1H 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).13C 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 C14H14N2O(M-H+):225.1033,found:225.1028.. This result further demonstrates the product molecular structure as described above for molecular structure 10.
Example 11
A preparation method of a 4-isopropyl-2-methylquinoline compound (a structural formula is shown as the following formula 11):
The photocatalyst Mes-Acr-PhBF 4 (0.01 mmol,4.6 mg), ammonium persulfate (0.5 mmol) and the capture reagent heterocycle 2-methylquinoline (0.2 mmol) were weighed into oven dried 8mL vials containing magnetic star bars. H 2 O (0.1 mL) and MeCN (0.9 mL) were added followed by the linear tertiary alcohol 3-methyl-2-phenylbutan-2-ol (0.4 mmol) and then trifluoroacetic acid (0.4 mmol). The reaction vessel was degassed and backfilled with argon and then placed in a SynLED x4 photoreactor (SynLED discoverTM 450 nm). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was quenched with 1N NaOH (10 mL). The combined organic layers were washed with brine, dried (Na 2SO4) and concentrated in vacuo. The crude product was purified by flash column over silica gel. Compound 11 yield 78%.
The results of the correlation characterization analysis were 1H 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).13C 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 C13H15N(M+H+):186.1277,found:186.1277.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 11.
Example 12
A preparation method of a 2-benzyl-3, 5, 6-trimethyl pyrazine compound (structural formula is shown in the following formula 12):
The linear tertiary alcohol was 2-methyl-1-phenyl-2-propanol, the trapping agent was 2,3, 5-trimethylpyrazine and the yield was 67% in the same manner as in example 11.
The results of the correlation characterization analysis were 1H 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).13C 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 C14H16N2(M+H+):213.1386,found:213.1386.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 12.
Example 13
A process for producing a 2-isopropylbenzo [ d ] thiazole compound (structural formula 13:
the linear tertiary alcohol is 3-methyl-2-phenyl butane-2-alcohol, and the capture reagent is benzothiazole; otherwise, the same procedure as in example 11 was carried out, with a yield of 83%.
The results of the correlation characterization analysis were 1H 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).13C 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 C10H11NS(M+H+):178.0685,found:178.0685.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 13.
Example 14
A method for preparing a 4-cyclohexyl-2, 6-lutidine compound (the structural formula is shown as the following formula 14):
The linear tertiary alcohol is 1-cyclohexyl-1-phenyl ethane-1-alcohol, and the capture reagent is 2, 6-dimethylpyridine; otherwise, the same procedure as in example 11 was carried out, with a yield of 51%.
The results of the correlation characterization analysis were 1H 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).13C 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 C13H19N(M+H+):190.1590,found:190.1589.. This result further demonstrates that the product molecular structure is as described above for molecular structure 14.
Example 15
A method for preparing a 2-cyclopentyl-4, 6-dimethylpyrimidine compound (structural formula shown as formula 15 below):
The linear tertiary alcohol is 1-cyclopentyl-1-phenylethan-1-ol, and the capture reagent is 4, 6-dimethylpyrimidine; otherwise, the same procedure as in example 11 was carried out, with a yield of 56%.
The results of the correlation characterization analysis were 1H 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).13C NMR(126MHz,Chloroform-d)δ173.70,166.29,117.25,48.98,33.07,25.95,24.05.HRMS(ESI-TOF)calculated for C11H16N2(M+H+):177.1386,found:177.1386.. This result further demonstrates that the product molecular structure is as described above for molecular structure 15.
Example 16
A method for preparing a 2-isopropyl-5-methylthiazole-4-carboxylic acid ethyl ester compound (the structural formula is shown as the following formula 16):
The linear tertiary alcohol is 3-methyl-2-phenyl butane-2-alcohol, and the capture reagent is 5-methylthiazole-4-carboxylic acid ethyl ester; otherwise, the same procedure as in example 11 was carried out, with a yield of 61%.
The results of the correlation characterization analysis were 1H 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).13C 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 C10H15NO2S(M+H+):214.0896,found:214.0896.. This result further demonstrates that the product molecular structure is as described above for molecular structure 16.
Example 17
A method for preparing a 2, 6-dichloro-8-isopropyl-9-methyl-9H-purine compound (structural formula shown in the following formula 17):
The linear tertiary alcohol was 3-methyl-2-phenylbutane-2-ol, the trapping agent was 2, 6-dichloro-9-methyl-9H-purine, and the yield was 76% in the same manner as in example 11.
The results of the correlation characterization analysis were 1H NMR(500MHz,Chloroform-d)δ3.83(s,3H),3.25(p,J＝6.9Hz,1H),1.47(d,J＝6.9Hz,6H).13C 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 C9H10Cl2N4(M+H+):245.0355,found:245.0356.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 17.
Example 18
A preparation method of 4, 4-dimethyl-2-phenyl methyl valerate compound (structural formula is shown as the following formula 18) comprises the following steps:
The photocatalyst Mes-Acr-PhBF 4 (0.01 mmol,4.6 mg) and the capture reagent methyl 2-phenylacrylate (0.4 mmol) were weighed into oven dried 8mL vials containing magnetic star bars. Anhydrous acetonitrile (1 mL) was added followed by 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 SynLED x4 photoreactor (SynLED discoverTM 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 give the target product in 73% yield.
The results of the correlation characterization analysis were 1H 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).13C 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 C14H20O2(M+H+):221.1536,found:221.1536.. This result further demonstrates that the product molecular structure is as described above for molecular structure 18.
Example 19
A method for preparing a (3, 3-dimethylbutane-1, 1-methylsulfonyl) benzene compound (structural formula is shown as the following formula 19):
The photocatalyst Mes-Acr-PhBF 4 (0.01 mmol,4.6 mg) and the capture reagent 1, 1-bis (benzenesulfonyl) ethylene (0.4 mmol) were weighed into oven-dried 8mL vials containing magnetic star bars. Anhydrous acetonitrile (1 mL) was added followed by 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 SynLED x4 photoreactor (SynLED discoverTM 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 give the desired product in 78% yield.
The results of the correlation characterization analysis were 1H 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).13C 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 C18H22O4S2(M-H+):365.0887,found:365.0886.. This result further demonstrates the product molecular structure as described above for molecular structure 19.
Example 20
A method for preparing a 2- (3, 3-dimethylbutyl) pyridine compound (structural formula shown in the following formula 20):
the photocatalyst Mes-Acr-PhBF 4 (0.01 mmol,4.6 mg) and the capture reagent 2-alkenylpyridine (0.4 mmol) were weighed into oven-dried 8mL vials containing magnetic star bars. Anhydrous acetonitrile (1 mL) was added followed by 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 SynLED x4 photoreactor (SynLED discoverTM 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 give the desired product in 77% yield.
The results of the correlation characterization analysis are 1H 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).13C 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 C11H17N(M+H+):164.1434,found:164.1434.. The results further confirm that the product molecular structure is as described above for molecular structure 20.
Example 21
A process for preparing (R) - (2- (tert-butyl) -6-methoxyquinolin-4-yl) ((1S, 2S,4S, 5R) -5-vinylquinolin-2-yl) methanol compound having the structural formula shown in formula 21:
the linear tertiary alcohol is 3, 3-dimethyl-2-phenyl butane-2-alcohol, and the capturing reagent is quinine; otherwise, the same procedure as in example 11 was carried out, with a yield of 60%.
The results of the correlation characterization analysis were 1H 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).13C 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 C24H32N2O2(M+H+):381.2537,found:381.2537.. This result further demonstrates that the molecular structure of the product is as described above for molecular structure 21.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.

Claims (3)

1. A photo-redox catalytic method, comprising the steps of:
providing a linear tertiary alcohol compound and a free radical trapping agent;
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 ；
Wherein n=an integer of 0 to 4, R 1、R2 and R 3 are each independently selected from any one of C 1-C20 alkyl, C 1-C20 heteroalkyl, C 3-C20 cycloalkyl, C 3-C20 heterocycloalkyl, C 2-C20 alkenyl, C 3-C20 cycloalkenyl, C 1-C20 alkoxy, C 6-C14 aryl, C 6-C14 aryl C 1-C20 alkyl, cyano C 1-C20 alkyl, C 1-C20 alkyloxycarbonyl C 1-C20 alkyl, C 3-C20 alkylsilyl, halogen, trifluoromethoxy, sulfonamide, and hydrogen atom; and R 2 and R 3 are not hydrogen atoms;
The free radical capture reagent is at least one selected from quinoline, 2-methylquinoline, quinine, pyridine, 2, 6-lutidine, thiazole, 5-methylthiazole-4-carboxylic acid ethyl ester, benzothiazole, pyrazine, 2,3, 5-trimethylpyrazine, pyrimidine, 4, 6-dimethylpyrimidine, purine, 2, 6-dichloro-9-methyl-9H-purine;
the photocatalyst is selected from acridine salt catalyst Mes-Acr-PhBF 4;
the catalytic reaction is also added with a Bronsted acid reagent, an oxidant and an acetonitrile solvent; the bronsted acid reagent is selected from fluoroacetic acid and the oxidizing agent is selected from persulfates.
2. The photo-redox catalytic method according to claim 1, wherein R 1、R2 and R 3 are each independently selected from any of C 1-C10 alkyl, C 1-C10 heteroalkyl, C 3-C10 cycloalkyl, C 3-C10 heterocycloalkyl, C 2-C10 alkenyl, C 3-C10 cycloalkenyl, C 1-C10 alkoxy, C 6-C14 aryl, C 6-C14 aryl C 1-C10 alkyl, cyano C 1-C10 alkyl, C 1-C10 alkyloxycarbonyl C 1-C10 alkyl and C 3-C10 alkylsilyl.
3. The photo-redox catalytic process according to any one of claims 1-2, wherein the molar ratio of the photocatalyst, the oxidant and the bronsted acid reagent is (0.1-20): 0.2-40.
CN202211378442.0A 2021-05-28 2021-05-28 Photooxidation reduction catalytic process Active CN115710199B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211378442.0A CN115710199B (en) 2021-05-28 2021-05-28 Photooxidation reduction catalytic process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110588659.3A CN113387837B (en) 2021-05-28 2021-05-28 Photo-oxidation-reduction catalysis method
CN202211378442.0A CN115710199B (en) 2021-05-28 2021-05-28 Photooxidation reduction catalytic process

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN202110588659.3A Division CN113387837B (en) 2021-05-28 2021-05-28 Photo-oxidation-reduction catalysis method

Publications (2)

Publication Number Publication Date
CN115710199A CN115710199A (en) 2023-02-24
CN115710199B true CN115710199B (en) 2024-06-28

Family

ID=77619330

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202110588659.3A Active CN113387837B (en) 2021-05-28 2021-05-28 Photo-oxidation-reduction catalysis method
CN202211378442.0A Active CN115710199B (en) 2021-05-28 2021-05-28 Photooxidation reduction catalytic process

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN202110588659.3A Active CN113387837B (en) 2021-05-28 2021-05-28 Photo-oxidation-reduction catalysis method

Country Status (1)

Country Link
CN (2) CN113387837B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108047230A (en) * 2017-12-29 2018-05-18 深圳蓝新科技有限公司 Pa Na replaces the preparation method of Buddhist nun
CN108329240A (en) * 2018-03-27 2018-07-27 深圳蓝新科技有限公司 The preparation method of florfenicol midbody

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019168874A1 (en) * 2018-02-27 2019-09-06 The Research Foundation For The State University Of New York Difluoromethoxylation and trifluoromethoxylation compositions and methods for synthesizing same
CN109293541B (en) * 2018-11-09 2020-10-27 闽南师范大学 Method for preparing alpha-aryl-gamma-methylsulfinylketone compound by visible light catalysis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108047230A (en) * 2017-12-29 2018-05-18 深圳蓝新科技有限公司 Pa Na replaces the preparation method of Buddhist nun
CN108329240A (en) * 2018-03-27 2018-07-27 深圳蓝新科技有限公司 The preparation method of florfenicol midbody

Also Published As

Publication number Publication date
CN115710199A (en) 2023-02-24
CN113387837A (en) 2021-09-14
CN113387837B (en) 2023-02-21

Similar Documents

Publication Publication Date Title
CN113912577B (en) Rockwell intermediate, rockwell and its derivative, and preparation and application
CN109896918B (en) Unsaturated carbonyl compound and preparation method and application thereof
CN109761897B (en) Method for copper-catalyzed alkylation of C (sp2) -H bond of N-heterocyclic aromatic hydrocarbon compound
CN113620762A (en) Ketene compound and preparation method and application thereof
CN115710199B (en) Photooxidation reduction catalytic process
CN110683926B (en) Preparation method of carboxylic acid aryl ester compound
CN109912579B (en) Preparation method of 2, 2-disubstituted tetrahydrofuran derivative
WO2021114424A1 (en) Method for preparing trifluorohydrocarbyl sulfone compound
CN114588929A (en) Supported copper nanocluster catalyst and application thereof in AHA coupling reaction
CN114773174A (en) Synthetic method of alpha-deuterated carbonyl compound
CN105237466B (en) A kind of method for synthesizing three substituted pyridine derivatives
JP6067700B2 (en) Alcohol oxidation catalyst and alcohol oxidation method using the same
CN116444330A (en) Addition product of alkyl free radical and capture reagent, addition method and application thereof
CN115745836A (en) Method for inducing reaction of alkyl neopentyl benzene and capture reagent by photocatalyst
CN115872900A (en) Method for generating and capturing alkyl free radical, product thereof and application of product
CN110713451B (en) Microwave radiation-assisted synthesis method of N-methyl-2-cyano-3, 4-disubstituted pyrrole compound
CN112961105B (en) Alkylation method of nitrogen-containing heterocyclic compound
CN109265391B (en) Biphenyl polysubstituted 1,2,5, 6-tetrahydropyridine compound and synthetic method and application thereof
CN112300059B (en) Preparation method of PF-06651600 intermediate
CN115433128B (en) Acridine tetrafluoroborate photoreaction catalyst and synthesis method thereof
CN110938086B (en) Half-sandwich ruthenium-thione complex and preparation method thereof, ammonia borane hydrolysis method and nitrobenzene compound reduction method
CN113651720B (en) Substituted alkenyl thiocyanate compound and preparation method thereof
CN112125843B (en) Preparation method of 3-hydroxymethyl-4-phenyl-3, 4-dihydroquinolinone compound
CN109942617B (en) Alpha-tetra-substituted chiral alkynone compound and preparation method and application thereof
CN109942612B (en) Diyne enamine compound and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant