Research Progress on Copper(I)-Catalyzed Asymmetric Allylation of Ketones or Ketimines DOI
Hui Li, Liang Yin

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(12), P. 1274 - 1274

Published: Jan. 1, 2024

Language: Английский

Recent Advances in Catalytic Asymmetric Ketone Allylations and Their Applications DOI

Lie Wang,

Ruoshi Jin, Yiyuan Peng

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1487 - 1513

Published: Jan. 9, 2025

Due to the wide applications of resulting chiral tertiary homoallylic alcohols in organic synthesis, catalytic asymmetric ketone allylations have attracted continuous attention from synthetic chemists. Despite inherent difficulty enantiofacial differentiation and low reactivity ketones, past two decades witnessed rapid progress allylation ketones. Many efficient methods been reported, with discovery unprecedented catalysts reagents. The current Review aims give a summary achievements this area 2011 date is divided into six parts according reagents that were applied. Special paid scope application each method brief introduction corresponding mechanisms.

Language: Английский

Citations

2

Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition DOI
Lingyun Yao, Xinlan Zou, Jian Zhang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5796 - 5805

Published: March 25, 2025

The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.

Language: Английский

Citations

1

Synthesis of chiral phosphine derivatives through a copper(I)-catalyzed desymmetric SNAr reaction DOI Creative Commons
Shuai Zhang, Peizhi Liu, Yanbo Li

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Language: Английский

Citations

0

Enantioselective Synthesis of α‐Hydroxy Allyl Ketones via BINAP‐CuH‐Catalyzed Hydroacylation DOI Open Access
Sundaram Maurya,

N. Navaneetha,

Prativa Behera

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations reveal that this reaction proceeds through nucleophilic attack kinetically favourable Z ‐selective allyl‐copper intermediate acid anhydrides six‐membered chair‐like transition state, stabilized by strongly non‐covalent interactions ultimately leads high level enantioselectivities using simple BINAP ligand. This successfully overcomes challenges over‐reduction carbonyl functionality presence CuH‐complex, olefin isomerization highly enolizable ‐stereocenter, which can lead erosion enantioselectivities, making our strategy desirable. The exhibits wide range substrate scope including symmetrical as well carbonic with both aromatic, aliphatic substitutions. In addition, ‐substituted provide exclusive syn α,α′ ‐disubstituted excellent enantiomeric ratios, where allylation occurs one carbonyls containing matched α‐ stereocenter, confirmed mechanistic studies.

Language: Английский

Citations

0

Enantioselective Synthesis of α‐Hydroxy Allyl Ketones via BINAP‐CuH‐Catalyzed Hydroacylation DOI Open Access
Sundaram Maurya,

N. Navaneetha,

Prativa Behera

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations reveal that this reaction proceeds through nucleophilic attack kinetically favourable Z ‐selective allyl‐copper intermediate acid anhydrides six‐membered chair‐like transition state, stabilized by strongly non‐covalent interactions ultimately leads high level enantioselectivities using simple BINAP ligand. This successfully overcomes challenges over‐reduction carbonyl functionality presence CuH‐complex, olefin isomerization highly enolizable ‐stereocenter, which can lead erosion enantioselectivities, making our strategy desirable. The exhibits wide range substrate scope including symmetrical as well carbonic with both aromatic, aliphatic substitutions. In addition, ‐substituted provide exclusive syn α,α′ ‐disubstituted excellent enantiomeric ratios, where allylation occurs one carbonyls containing matched α‐ stereocenter, confirmed mechanistic studies.

Language: Английский

Citations

0

BINAP-CuH-catalysed enantioselective allylation using alkoxyallenes to access 1,2-syn-tert,sec-diols DOI Creative Commons

N. Navaneetha,

Sundaram Maurya, Prativa Behera

et al.

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

Published: Jan. 1, 2024

An economical method for highly enantioselective and diastereoselective synthesis of 1,2- syn-tert , sec -diols via Cu-BINAP-catalysed reductive coupling alkoxyallenes with ketones.

Language: Английский

Citations

2

Asymmetric Synthesis of Trisubstituted Vicinal Diols through Copper(I)-Catalyzed Diastereoselective and EnantioselectiveAllylation of Ketones with Siloxypropadienes DOI
Jinlong Zhang, Gaoxi Jiang

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(7), P. 2391 - 2391

Published: Jan. 1, 2024

Language: Английский

Citations

0

Research Progress on Copper(I)-Catalyzed Asymmetric Allylation of Ketones or Ketimines DOI
Hui Li, Liang Yin

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(12), P. 1274 - 1274

Published: Jan. 1, 2024

Language: Английский

Citations

0