Organic Letters, Год журнала: 2024, Номер 26(2), С. 542 - 546
Опубликована: Янв. 8, 2024
Electrocarboxylation of the C(sp3)–O bond in 1,3-oxazolidin-2-ones with CO2 to achieve β-amino acids is developed. The C–O substrates can be selectively cleaved via single electron transfer on surface a cathode or through CO2• – intermediate under additive-free conditions. A great diversity obtained moderate excellent yield and readily converted various biologically active compounds.
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
144
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
139
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
77
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
63
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
61
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)
Опубликована: Сен. 12, 2023
Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.
Язык: Английский
Процитировано
48
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10967 - 10973
Опубликована: Апрель 19, 2023
Despite the widespread applications of α-hydroxyalkyl cyclic amines, direct and diverse access to such a class unique vicinal amino alcohols still remains, date, challenge. Here, through strategy electroreductive α-hydroxyalkylation inactive N-heteroarenes with ketones or electron-rich arylaldehydes, we describe room temperature approach for construction which features broad substrate scope, operational simplicity, high chemoselectivity, no need pressurized H2 gas transition metal catalysts. The zinc ion generated from anode oxidation plays crucial role in activation both reactants by decreasing their reduction potentials. electroreduction combination Lewis acids this work is anticipated develop more useful transformations.
Язык: Английский
Процитировано
47
Nature Catalysis, Год журнала: 2024, Номер 7(4), С. 412 - 421
Опубликована: Фев. 23, 2024
Язык: Английский
Процитировано
30
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
Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(4)
Опубликована: Окт. 24, 2022
Alcohols and their derivatives are ubiquitous versatile motifs in organic synthesis. Deoxygenative transformations of these compounds often challenging due to the thermodynamic penalty associated with cleavage C-O bond. However, electrochemically driven redox events have been shown facilitate bond alcohols either through direct electron transfer or use mediators electroactive catalysts. Herein, a comprehensive overview preparative mediated protocols for activation functionalization is detailed, including indirect electrosynthetic methods, as well photoelectrochemical strategies.
Язык: Английский
Процитировано
55