Synergistic Ni/Pd Catalysis for Asymmetric Allylic Alkylation of 2-Acyl Imidazoles DOI
Fan Wu, Zhiming Li, Chao Fu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(29), P. 5448 - 5453

Published: July 14, 2023

The asymmetric α-allylation of α-aryl-substituted 2-acetyl imidazoles synergistically catalyzed by Ni/Pd catalysts has been developed. In this process, the nickel-bisoxazoline complex activates enolate an acetyl imidazole, which then reacts with a π-allyl palladium electrophile generated from allyl alcohol derivative palladium-based catalyst. A broad scope substrates was suitable for reaction. utility method demonstrated gram-scale reaction and subsequent elaboration allylation products.

Language: Английский

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

144
Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides DOI Creative Commons

Yun-Zhao Wang,

Zhenhua Wang, Inbal Lorena Eshel

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Language: Английский

Citations

57
Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp3)–C(sp3) Cross Coupling DOI
Yang Gao,

Benxiang Zhang,

Jiayan He

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11518 - 11523

Published: May 16, 2023

The first examples of enantioselective doubly decarboxylative cross coupling are disclosed. Malonate half amides smoothly coupled to a variety primary carboxylic acids after formation the corresponding redox-active esters under Ni-electrocatalytic conditions using new chiral ligand based on PyBox, resulting in with α-alkylated stereocenters. scope reaction is broad, tolerating numerous functional groups, and uniformly proceeds high ee. Finally, potential utility this radical–radical reductive simplify synthesis demonstrated case studies.

Language: Английский

Citations

51
The applications of electrochemical synthesis in asymmetric catalysis DOI

Ke‐Jin Jiao,

Zhenhua Wang, Cong Ma

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 3019 - 3047

Published: Oct. 27, 2022

Language: Английский

Citations

61
Cobaltaelectro-Catalyzed C–H Annulation with Allenes for Atropochiral and P-Stereogenic Compounds: Late-Stage Diversification and Continuous Flow Scale-Up DOI Creative Commons
Lin Ye, Tristan von Münchow, Lutz Ackermann

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9713 - 9723

Published: July 11, 2023

The 3d metallaelectro-catalyzed C-H activation has been identified as an increasingly viable strategy to access valuable organic molecules in a resource-economic fashion under exceedingly mild reaction conditions. However, the development of enantioselective is very challenging and its infancy. Here, we disclose merger cobaltaelectro-catalyzed with asymmetric catalysis for highly annulation allenes. A broad range C-N axially chiral P-stereogenic compounds were thereby obtained good yields up 98% high enantioselectivities >99% ee. practicality this approach was demonstrated by diversification complex bioactive drug well decagram scale electrocatalysis continuous flow.

Language: Английский

Citations

41
Mixed-Linker Chiral 2D Covalent Organic Frameworks with Controlled Layer Stacking for Electrochemical Asymmetric Catalysis DOI
Yuan Chen,

Shiguo Fu,

Xing Kang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 635 - 645

Published: Dec. 26, 2023

Covalent organic frameworks (COFs) have undergone extensive research as heterogeneous catalysts for a wide range of significant reactions, but they not yet been investigated in the realm electrochemical asymmetric catalysis, despite their recognition an economical and sustainable strategy producing enantiopure compounds. Here, we report mixed-linker to design multicomponent two-dimensional (2D) chiral COFs with tunable layer stacking highly enantioselective electrocatalysis. By crystallizing mixtures triamines without MacMillan imidazolidinone catalyst or aryl substituent (ethyl isopropyl) dialdehyde derivative thieno-[3,2-

Language: Английский

Citations

41
Enantioselective nickel-catalysed electrochemical cross-dehydrogenative amination DOI
Kang Liang, Qinglin Zhang, Chang Guo

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(12), P. 1184 - 1193

Published: July 31, 2023

Language: Английский

Citations

34
Unlocking the Potential of Oxidative Asymmetric Catalysis with Continuous Flow Electrochemistry DOI
Pengyu Chen, Chong Huang,

Lianghua Jie

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7178 - 7184

Published: March 11, 2024

In the field of catalytic asymmetric synthesis, less-treated path lies in oxidative transformations. The hurdles pinpointing appropriate chemical oxidants and addressing their compatibility issues with catalysts functionalities present significant challenges. Organic electrochemistry, employing traceless electrons for redox reactions, is underscored as a promising solution. However, commonly used electrolysis batch cells introduces its own set challenges, hindering advancement electrochemical catalysis. Here we introduce microfluidic electrochemistry platform single-pass continuous flow reactors that exhibits wide-ranging applicability to various This exemplified through sulfenylation 1,3-dicarbonyls, dehydrogenative C–C coupling, alkene annulation processes. unique properties not only eliminate need but also enhance reaction efficiency reduce use additives electrolytes. These salient features expedite discovery development addition, production facilitated by parallel ensures straightforward upscaling, removing necessity reoptimization across scales, evidenced direct translation from milligram screening hectogram synthesis.

Language: Английский

Citations

16
Electrochemical Asymmetric Radical Functionalization of Aldehydes Enabled by a Redox Shuttle DOI Creative Commons
Daniele Mazzarella,

Chun Qi,

Michael Vanzella

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 16, 2024

Aminocatalysis is a well-established tool that enables the production of enantioenriched compounds under mild conditions. Its versatility underscored by its seamless integration with various synthetic approaches. While combination aminocatalysis metal catalysis, photochemistry, and stoichiometric oxidants has been extensively explored, synergy electrochemical activation remains largely unexplored. Herein, we present successful merger electrochemistry to perform SOMO-type transformations, expanding toolkit for asymmetric synthesis. The methodology harnesses electricity drive oxidation catalytically generated enamines, which ultimately partake in enantioselective radical processes, leading α-alkylated aldehydes. Crucially, mechanistic studies highlight how this strategy enabled use redox shuttle, 4,4'-dimethoxybiphenyl, prevent catalyst degradation furnishing coveted good yield high enantioselectivity.

Language: Английский

Citations

14
Enantioselective Multicomponent Electrochemical Difunctionalization of Terminal Alkynes DOI

Qiannan Wang,

Xinyu Wang, Yong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The direct functionalization of alkyne triple bonds using a radical strategy provides an efficient platform for creating wide range substituted alkenes. However, developing multicomponent enantioselective reaction feedstock alkynes to forge all-carbon quaternary stereocenters─while addressing challenges related compatibility, selectivity, and efficiency─remains relatively rare. Here we report electrochemical nickel-catalyzed three-component cross-coupling readily available terminal alkynes, diverse racemic alkyl precursors, group transfer reagents (such as (TMS)3Si-H, RSe-SeR, RTe-TeR, CHI3), achieving excellent regio-, stereo-, enantioselectivities (more than 70 examples, up 95% ee). Electricity-mediated difunctionalizations significantly expand the scope both aliphatic aromatic demonstrating functional compatibility. key success lies in rational design anodically generated nickel-bound tertiary intermediates, which stereoselectively capture form vinyl radicals participate subsequently processes enable intermolecular anti-stereoselective difunctionalization alkynes. This approach allows transformation into structural entities with α-quaternary stereogenic centers.

Language: Английский

Citations

1