Organic Chemistry Frontiers, Год журнала: 2022, Номер 10(3), С. 624 - 631
Опубликована: Дек. 17, 2022
A photo-induced redox cascade reaction has been developed for the chemoselective construction of isoxazolidine derivatives from stable and easily available nitroarenes amines.
Язык: Английский
eScience, Год журнала: 2022, Номер 2(3), С. 243 - 277
Опубликована: Апрель 23, 2022
Compared with general redox chemistry, electrochemistry using the electron as a potent, controllable, yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis. With its environmentally benign features gradually being uncovered and studied, electrosynthesis is currently undergoing revival becoming rapidly growing area within synthetic community. Among electrochemical transformations, anodically enabled ones have been far extensively exploited than those driven by cathodic reduction, although both approaches are conceptually attractive. To stimulate development of cathodically reactions, this review summarizes recently developed reductive electrosynthetic protocols, discussing highlighting reaction features, substrate scopes, applications, plausible mechanisms reveal recent trends in area. Herein, reduction-enabled preparative transformations categorized into four types: reduction (1) unsaturated hydrocarbons, (2) heteroatom-containing carbon-based systems, (3) saturated C-hetero or C–C polar/strained bonds, (4) hetero-hetero linkages. Apart from net electroreductive few examples photo-electrosynthesis well paired electrolysis also introduced, which offer opportunities overcome certain limitations improve versatility. The electrochemically driven, transition metal-catalyzed cross-couplings that comprehensively discussed several other reviews not included here.
Язык: Английский
Процитировано
140
Science, Год журнала: 2023, Номер 381(6665), С. 1474 - 1479
Опубликована: Сен. 28, 2023
Nitrogen scanning in aryl fragments is a valuable aspect of the drug discovery process, but current strategies require time-intensive, parallel, bottom-up synthesis each pyridyl isomer because lack direct carbon-to-nitrogen (C-to-N) replacement reactions. We report site-directable C-to-N reaction allowing unified access to various pyridine isomers through nitrene-internalization process. In two-step, one-pot procedure, azides are first photochemically converted 3
Язык: Английский
Процитировано
96
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: 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
Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(16), С. 1913 - 1928
Опубликована: Апрель 24, 2024
Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.
Язык: Английский
Процитировано
26
Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(17)
Опубликована: Июль 6, 2022
Abstract Carbon dioxide (CO 2 ) is an abundant, inexpensive, renewable C1 resource and the main component of greenhouse gas, thereby research for its sustainable efficient conversion has received notable attention in recent years. Electrochemical organic synthesis, as a green synthetic method, convinced to be ideal approach CO utilization. In this review, advances electrocarboxylation with were summarized through different reaction types, which would disclose great potential synthesis.
Язык: Английский
Процитировано
70
Organic Letters, Год журнала: 2021, Номер 23(9), С. 3472 - 3476
Опубликована: Апрель 16, 2021
An electroreductive arylation reaction of aliphatic and aromatic aldehydes as well ketones with electro-deficient (hetero)arenes is described. A variety cyano(hetero)arenes carbonyl compounds, especially aldehydes, have been examined, providing secondary tertiary alcohols in moderate to good yields. Mechanistic studies, including cyclic voltammetry (CV), electron paramagnetic resonance (EPR), divided-cell experiments, support the generation ketyl radicals persistent heteroaryl radical anions via cathodic reduction followed by radical-radical cross-coupling.
Язык: Английский
Процитировано
64
Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 263 - 316
Опубликована: Дек. 7, 2023
The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)
Язык: Английский
Процитировано
44
Chemistry - A European Journal, Год журнала: 2024, Номер unknown
Опубликована: Июль 16, 2024
The advancement in electrochemical techniques has unlocked a new path for achieving unprecedented oxidations and reductions of aryl radical precursors controlled selective manner. This approach facilitates the construction aromatic carbon-carbon carbon-heteroatom bonds. In light green merits growing importance this technique chemistry, review aims to provide an overview recent advance generation radicals organized by precursor type, with focus on substrate scope, limitation, underlying mechanism, thereby inspiring future work generation.
Язык: Английский
Процитировано
11
Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(34), С. 6707 - 6720
Опубликована: Янв. 1, 2022
Fluorinated organic compounds are common among pharmaceuticals, agrochemicals and materials. The significant strength of the C-F bond results in chemical inertness that, depending on context, is beneficial, problematic or simply a formidable synthetic challenge. Electrosynthesis rapidly expanding methodology that can enable new reactivity selectivity for cleavage formation bonds. Here, comprehensive overview synthetically relevant electrochemically driven protocols activation functionalization presented, including photoelectrochemical strategies.
Язык: Английский
Процитировано
39