Acid/Base-Tuned Asymmetric Reductive Heck and Denitrogenative Heck Reactions of In Situ-Formed α,β-Unsaturated Hydrazone DOI

Shuling Yu,

Xiaoyu Zhou, Xiaofeng Tong

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 72 - 80

Published: Dec. 13, 2024

Despite significant progress in the catalytic asymmetric 1,4-additions between various Michael donors and acceptors, exploration of organohalide remains elusive. Herein, we report Pd(0)-catalyzed intramolecular vinyl/aryl iodides to α,β-unsaturated hydrazones, featuring situ-formed hydrazone acid/base-tuned reaction pathways. Due its strong coordination ability, is capable steering C–C bond formation follow 1,4-addition mechanism instead conventional alkene insertion, thus enabling generation vinylhydrazinyl–Pd2+ species via Zimmerman–Traxler chairlike transition state. Notably, this preferentially undergoes protonation under acidic conditions, furnishing a reductive Heck with aid native hydrazine reductant, while it susceptible β-HN elimination basic conditions achieve denitrogenative reaction. The protocol affords highly enantioselective access diverse heterocycles, groups poised for further chemical manipulations.

Language: Английский

Nickel(ii)-hydrazineylpyridine catalyzed regioselective synthesis of α-benzyl substituted β-hydroxy ketones via a Fenton free radical reaction DOI
Apurva Singh, Naseem Ahmed

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Ni-PyH-catalyzed regioselective synthesis of α-benzyl substituted β-hydroxy ketones is reported via a Fenton free-radical reaction. Protocol enables facile access to products in good excellent yields toluene at room temperature 100 °C.

Language: Английский

Citations

0
Cobalt-Catalyzed Enantioselective Reductive Arylation, Heteroarylation, and Alkenylation of Michael Acceptors via an Elementary Mechanism of 1,4-Addition DOI
Mengxin Zhao, Wenqiang Xu, Yun‐Dong Wu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20477 - 20493

Published: July 10, 2024

Cobalt complexes with chiral quinox ligands effectively promote the enantioselective conjugate addition of enones using aryl, heteroaryl, and alkenyl halides sulfonates. Additionally, a cobalt complex strongly donating diphosphine, BenzP*, successfully catalyzes asymmetric reductive arylation alkenylation α,β-unsaturated amides. Both catalytic systems show broad scopes tolerance sensitive functional groups. reactions can be scaled up low loadings catalysts. Experimental results density theory (DFT) calculations suggest new mechanism elementary 1,4-addition aryl cobalt(I) complexes.

Language: Английский

Citations

3
Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones DOI Creative Commons
Zenghui Ye, Weiyuan Ma, Xi Zhang

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Abstract Herein, the study reports first electrochemical nickel‐catalyzed enantioselective hydro‐arylation/alkenylation of enones in an undivided cell with low‐cost electrodes absence external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides are employed as electrophiles for efficient preparation more than 56 valuable β‐arylated/alkenylated ketones a simple manner (up to 97% yield, ee). With advantages electrochemistry, excellent functional group tolerance late‐stage modification complex natural products pharmaceuticals made established protocol greener economic. Mechanism investigation suggests that Ni I /Ni III cycle may be involved this electro‐reductive reaction rather metal reductant driven 0 II cycle. Overall, activation turnover nickel catalyst avoid drawbacks posed by employment stoichiometric amount sensitive powder reductants.

Language: Английский

Citations

2
Nickel-Catalyzed Reductive Alkenylation of Enol Derivatives: A Versatile Tool for Alkene Construction DOI
Zhenzhen Zhao, Peng Guo,

Xiaobo Pang

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(22), P. 3356 - 3374

Published: Nov. 1, 2024

ConspectusKetone-to-alkene transformations are essential in organic synthesis, and transition-metal-catalyzed cross-coupling reactions involving enol derivatives have become powerful tools to achieve this goal. While substantial progress has been made nucleophile-electrophile reactions, recent developments nickel-catalyzed reductive alkenylation garnered increasing attention. These methods accommodate a broad range of functional groups such as aldehyde, ketone, amide, alcohol, alkyne, heterocycles, organotin compounds, providing an efficient strategy access structurally diverse alkenes. This Account primarily highlights the contributions from our laboratory growing field while also acknowledging key other researchers.Our early efforts area focused on coupling radical-active substrates, α-chloroboronates. method follows conventional radical chain mechanism, resulting facile valuable allylboronates. Encouraged by these promising results, we subsequently expanded substrate scope encompass radical-inactive compounds. By developing new strategies for controlling cross-selectivity, enabled Csp

Language: Английский

Citations

2
Cobalt-Catalyzed Enantioselective Reductive Addition of Ketimine with Cyclopropyl Chloride to Construct the Chiral Amino Esters Bearing Cyclopropyl Fragments DOI
Jiangtao Hu, Tingting Xia, Xianqing Wu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(22), P. 6311 - 6318

Published: Jan. 1, 2024

Co-catalyzed asymmetric reductive addition of ketimine with cyclopropyl chloride has been realized to access diverse chiral amino esters bearing fragments broad functional group tolerance and excellent enantioselectivities.

Language: Английский

Citations

1
Oxazaborolidine Catalyzed Asymmetric 1,4-Addition of Diarylphosphine Oxides to α,β-Unsaturated N-Acylindoles and N-Acylpyrroles DOI

Jinyi Qian,

Wendi Shao,

Qi Gao

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: unknown, P. 134331 - 134331

Published: Oct. 1, 2024

Language: Английский

Citations

0
Enantioselective Nickel-Catalyzed Electrochemical Reductive Conjugate Alkenylation of α,β-Unsaturated Ketones DOI Creative Commons
Siriphong Somprasong, Baonian Wan, Syuzanna R. Harutyunyan

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 20, 2024

We present an asymmetric electrochemical nickel-catalysed reductive conjugate addition of alkenyl bromides/aryl iodides to α,β-unsaturated ketones in undivided cell, which afforded β-alkenylate/arylate high yields with excellent enantioselectivities.

Language: Английский

Citations

0
Acid/Base-Tuned Asymmetric Reductive Heck and Denitrogenative Heck Reactions of In Situ-Formed α,β-Unsaturated Hydrazone DOI

Shuling Yu,

Xiaoyu Zhou, Xiaofeng Tong

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 72 - 80

Published: Dec. 13, 2024

Despite significant progress in the catalytic asymmetric 1,4-additions between various Michael donors and acceptors, exploration of organohalide remains elusive. Herein, we report Pd(0)-catalyzed intramolecular vinyl/aryl iodides to α,β-unsaturated hydrazones, featuring situ-formed hydrazone acid/base-tuned reaction pathways. Due its strong coordination ability, is capable steering C–C bond formation follow 1,4-addition mechanism instead conventional alkene insertion, thus enabling generation vinylhydrazinyl–Pd2+ species via Zimmerman–Traxler chairlike transition state. Notably, this preferentially undergoes protonation under acidic conditions, furnishing a reductive Heck with aid native hydrazine reductant, while it susceptible β-HN elimination basic conditions achieve denitrogenative reaction. The protocol affords highly enantioselective access diverse heterocycles, groups poised for further chemical manipulations.

Language: Английский

Citations

0