Regioselective Ni-Catalyzed reductive alkylsilylation of acrylonitrile with unactivated alkyl bromides and chlorosilanes DOI Creative Commons
Jinwei Sun, Yongze Zhou, Rui Gu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 19, 2022

Abstract Transition-metal catalyzed carbosilylation of alkenes using carbon electrophiles and silylmetal (-B, -Zn) reagents as the nucleophiles offers a powerful strategy for synthesizing organosilicones, by incorporating silyl groups across on C-C double bonds in one step. However, to best our knowledge, study silylative difunctionalization based remains underdeveloped. Herein, we present an example alkylation activated olefins with unactivated alkyl bromides chlorosilanes under nickel catalysis. The main feature this protocol is employing more easily accessible substrates including primary, secondary tertiary bromides, well various without pre-generated organometallics. A wide range alkylsilanes diverse structures can be efficiently assembled single step, highlighting good functionality tolerance approach. Furthermore, successful functionalization bioactive molecules synthetic applications method demonstrate its practicability.

Language: Английский

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency DOI
Guglielmo Coppola, Serena Pillitteri, Erik V. Van der Eycken

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(6), P. 2313 - 2382

Published: Jan. 1, 2022

Visible-light photoredox catalysis has been regarded as an extremely powerful tool in organic chemistry, bringing the spotlight back to radical processes. The versatility of photocatalyzed reactions already demonstrated be effective providing alternative routes for cross-coupling well multicomponent reactions. photocatalyst allows generation high-energy intermediates through light irradiation rather than using highly reactive reagents or harsh reaction conditions. In a similar vein, electrochemistry experienced fruitful renaissance generating without need any catalyst. Such milder approaches pose basis toward higher selectivity and broader applicability. electrochemical reactions, species acts starter cascade events. This diverse reactivity use is usually not covered by classical methods. Owing availability cheaper more standardized photo- reactors, easily scalable flow-setups, it surprising that these two fields have become areas increased research interest. Keeping view, this review aimed at overview synthetic design MCRs involving and/or activation crucial step with particular focus on choice difunctionalized reagent.

Language: Английский

Citations

167

Electrochemical Late-Stage Functionalization DOI Creative Commons
Yulei Wang, Suman Dana, Hao Long

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 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.

Language: Английский

Citations

146

Organoelectrophotocatalytic C–H Silylation of Heteroarenes DOI

Qinhui Wan,

Zhong‐Wei Hou,

Xin‐Ru Zhao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(6), P. 1008 - 1013

Published: Feb. 3, 2023

An organoelectrophotocatalytic approach for the C-H silylation of heteroarenes through dehydrogenation cross-coupling with H2 evolution has been developed. The strategy is carried out under a simple and efficient monocatalytic system by employing 9,10-phenanthrenequinone both as an organocatalyst hydrogen atom transfer (HAT) reagent, which avoids need external HAT oxidant, or metal reagent. A variety can be compatible in satisfactory yields excellent regioselectivity.

Language: Английский

Citations

64

Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes DOI

Keming Yang,

Tian Feng, Youai Qiu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 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.

Language: Английский

Citations

49

Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp3)/Si–H Functionalization and Hydrofunctionalization of Alkenes DOI Creative Commons
Sheng Zhang, Michael Findlater

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8731 - 8751

Published: June 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Language: Английский

Citations

48

Electrochemical Desaturative β‐Acylation of Cyclic N‐Aryl Amines DOI
Tian Feng, Siyi Wang, Yin Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(6)

Published: Dec. 8, 2021

Abstract Herein, we disclose a straightforward, robust, and simple route to access β‐substituted desaturated cyclic amines via an electrochemically driven desaturative β‐functionalization of amines. This transformation is based on multiple single‐electron oxidation processes using catalytic amounts ferrocene. The reaction proceeds in the absence stoichiometric electrolyte under mild conditions, affording desired products with high chemo‐ regioselectivity. was tolerant broad range substrates also enables late‐stage β‐C(sp 3 )−H acylation potentially valuable products. Preliminary mechanistic studies voltammetry reveal key role ferrocene as redox mediator reaction.

Language: Английский

Citations

81

Recent advances in photo- and electro-enabled radical silylation DOI
Liqing Ren, Na Li, Jie Ke

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(22), P. 6400 - 6415

Published: Jan. 1, 2022

This review aims to highlight the recent advances in area of radical type silylation reactions mediated by photo- and electrocatalysis.

Language: Английский

Citations

64

Salt‐Stabilized Silylzinc Pivalates for Nickel‐Catalyzed Carbosilylation of Alkenes DOI
Jixin Wang,

Zhili Duan,

Xingchen Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Feb. 18, 2022

Abstract We herein report the preparation of solid and salt‐stabilized silylzinc pivalates from corresponding silyllithium reagents via transmetalation with Zn(OPiv) 2 . These resulting organosilylzinc show enhanced air moisture stability unique reactivity in silylative difunctionalization alkenes. Thus, a practical chelation‐assisted nickel‐catalyzed regioselective alkyl benzylsilylation alkenes has been developed, which provides an easy method to access silanes broad substrate scope wide functional group compatibility. Kinetic experiments highlight that OPiv‐coordination is crucial improve pivalates. Furthermore, late‐stage functionalizations druglike molecules versatile modifications products illustrate synthetical utility this protocol.

Language: Английский

Citations

44

Organophotoelectrochemical silylation cyclization for the synthesis of silylated 3-CF3-2-oxindoles DOI

Qinhui Wan,

Chen-Yin Huang,

Zhong‐Wei Hou

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(14), P. 3585 - 3590

Published: Jan. 1, 2023

An organophotoelectrochemical approach for silylation cyclization of CF3-substituted N -arylacrylamides with organosilanes under transition-metal-free and oxidant-free conditions has been developed.

Language: Английский

Citations

44

Chloride‐Promoted Photoelectrochemical C—H Silylation of Heteroarenes DOI

Xin‐Ru Zhao,

Yu‐Chen Zhang,

Zhong‐Wei Hou

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(22), P. 2963 - 2968

Published: June 24, 2023

Comprehensive Summary A photoelectrochemical approach for the C—H silylation of heteroarenes through dehydrogenation cross‐coupling with H 2 evolution has been developed. The depends on hydrogen atom transfer (HAT) from silanes to Cl‐radical generated light‐induced homolytic cleavage Cl , in which was produced by electrochemical oxidation chloride. large number silylated heterocyclic molecules are rapidly constructed satisfactory yields without relying oxidants and metal reagents.

Language: Английский

Citations

40