Green Chemistry, Год журнала: 2023, Номер 25(7), С. 2681 - 2689
Опубликована: Янв. 1, 2023
Herein, a straightforward route for dual α,β-C(sp 3 )–H functionalized cyclic N -aryl amines using combination of electrocatalysis and iron catalysis is disclosed, setting the stage challenging multiple site selective C–H functionalization.
Язык: Английский
Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335
Опубликована: Сен. 26, 2023
Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.
Язык: Английский
Процитировано
146
Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(41)
Опубликована: Авг. 26, 2022
Herein, an electroreductive carboxylation of organic carbon-halogen bonds (X=Br and Cl) promoted by catalytic amounts naphthalene as mediator is reported. This transformation proceeds smoothly under mild conditions with a broad substrate scope 59 examples, affording the valuable versatile carboxylic acids in moderate to excellent yields without need costly transition metal, wasted stoichiometric metal reductants, or sacrificial anodes. Further late-stage carboxylations natural product drug derivatives demonstrate its synthetic utility. Mechanistic studies confirmed activation via single-electron transfer key role this reaction.
Язык: Английский
Процитировано
88
Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)
Опубликована: Июль 30, 2022
Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides CO 2 with high chemo‐ regioselectivity under mild sustainable electrochemical conditions is described. This showed broad substrate scope good functional‐group compatibility. In addition epoxides, four‐ six‐membered cyclic ethers could all be tolerated in the reaction provide synthetically useful hydroxy acids efficiency. Further late‐stage carboxylation of complex molecules drug demonstrated its potential application pharmaceutical industry. Mechanistic studies disclosed possible pathways.
Язык: Английский
Процитировано
78
Green Chemistry, Год журнала: 2023, Номер 25(17), С. 6538 - 6560
Опубликована: Янв. 1, 2023
An activation toolbox for the effective catalytic conversion of CO 2 to chemicals is proposed along with challenges and prospects related future development this exciting technology.
Язык: Английский
Процитировано
66
Chemical Society Reviews, Год журнала: 2023, Номер 52(4), С. 1168 - 1188
Опубликована: Янв. 1, 2023
This review focuses on recent advances in sacrificial anode-enabled organic electroreductions.
Язык: Английский
Процитировано
64
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)
Опубликована: Апрель 3, 2023
Carboxylation of easily available alkenes with CO2 is highly important to afford value-added carboxylic acids. Although dicarboxylation activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging unactivated 1,n-dienes (n>3) remains unexplored. Herein, we report first skipped dienes via electrochemistry, affording valuable dicarboxylic Control experiments and DFT calculations support single electron transfer (SET) reduction its radical anion, which followed by sluggish addition SET unstabilized alkyl radicals carbanions nucleophilic attack on give desired products. This reaction features mild conditions, broad substrate scope, facile derivations products promising application in polymer chemistry.
Язык: Английский
Процитировано
62
Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 5227 - 5420
Опубликована: Апрель 25, 2024
Ionic liquids (ILs) have unique physicochemical properties that make them advantageous for catalysis, such as low vapor pressure, non-flammability, high thermal and chemical stabilities, the ability to enhance activity stability of (bio)catalysts. ILs can improve efficiency, selectivity, sustainability bio(transformations) by acting activators enzymes, selectively dissolving substrates products, reducing toxicity. They also be recycled reused multiple times without losing their effectiveness. based on imidazolium cation are preferred structural organization aspects, with a semiorganized layer surrounding catalyst. act container, providing confined space allows modulation electronic geometric effects, miscibility reactants residence time species. stabilize ionic radical species control catalytic dynamic processes. Supported IL phase (SILP) derivatives polymeric (PILs) good options molecular engineering greener The major factors governing metal, photo-, electro-, biocatalysts in discussed detail vast literature available over past two half decades. Catalytic reactions, ranging from hydrogenation cross-coupling oxidations, promoted homogeneous heterogeneous catalysts both single multiphase conditions, extensively reviewed considering knowledge accumulated until now.
Язык: Английский
Процитировано
52
ACS Catalysis, Год журнала: 2023, Номер 13(4), С. 2482 - 2488
Опубликована: Фев. 3, 2023
The radical anion of CO2 (CO2•–) is a strongly nucleophilic species with rapidly emerging applications in contemporary organic chemistry. This exhibits high reactivity single-electron reduction reactions due to the concomitant release stable CO2, or Giese-type reactions, especially for electron-deficient alkenes and styrene derivatives. In contrast previous reports, we herein disclose development robust method introduction CO2•–, which can be generated from cesium formate under photoredox/hydrogen atom transfer (HAT) catalysis, into heteroaromatics such as benzofuran, benzothiophene, indole derivatives afford synthetically useful α-oxy, α-thio, α-amino acid moderate yield. addition, when using naphthalene derivatives, both addition occur simultaneously produce carboxylated tetrahydronaphthalene good Moreover, one tetrahydronaphthalenes that bear cyano group was transformed corresponding γ-butyrolactam via functionality through hydrogenation followed by cyclization. To best our knowledge, these dearomative carboxylation metal formates photoredox/HAT conditions are unprecedented, thus providing synthetic option C1 source (hetero)aromatics.
Язык: Английский
Процитировано
50
Accounts of Chemical Research, Год журнала: 2024, Номер 57(18), С. 2728 - 2745
Опубликована: Сен. 3, 2024
ConspectusCarbon dioxide (CO
Процитировано
36
Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2249 - 2266
Опубликована: Май 15, 2024
Comprehensive Summary CO 2 is an abundant, nontoxic, and renewable C1 feedstock in synthetic chemistry. Direct carboxylation of readily available olefins incorporating regarded as a promising strategy to access high value‐added carboxylic acids well fixation. However, due the thermodynamic stability kinetic inertness difficulty controlling regioselectivity, with still remains challenging. Radical‐type functionalization represented powerful protocol enabled development novel transformations this realm. More recently, advance new technology, such photoredox catalysis renaissance electrochemistry organic synthesis, offered unique chemical reactivities radical precursors provided solutions olefins. This review presents recent advances radical‐type olefins, which has mainly been achieved through photocatalysis electrocatalysis last decade. In article, we provide comprehensive introduction progress, summarize advantages limitations current research, discuss potential outlook for further development. Key Scientists
Язык: Английский
Процитировано
19