Mechanistic Study of Ni and Cu Dual Catalyst for Asymmetric C–C Bond Formation; Asymmetric Coupling of 1,3-Dienes with C-nucleophiles to Construct Vicinal Stereocenters DOI

Jingzhao Xia,

Takahiro Hirai, Shoichiro Katayama

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6643 - 6655

Published: May 21, 2021

We report details of the reaction mechanism for a coupling 1,3-dienes with C-nucleophiles that was catalyzed by Ni/Cu cooperative catalyst system using Ni(cod)2 and [Cu(CH3CN)4]PF6 in presence chiral JOSIPHOS-type bisphosphine ligand iPr2NEt, providing direct access to highly valuable vicinal quaternary tertiary stereocenters high enantio- diastereoselectivity. The bimetallic exhibited broad substrate scope, including both cyclic/acyclic stabilized nucleophiles aryl-/alkyl-substituted 1,3-dienes. elucidated depth isolating characterizing four key complexes nickel copper conducting deuterium labeling experiments, kinetic studies, density functional theory calculations. turnover-limiting step this is proton-transfer diene-coordinated Ni complex 6 from cationic Cu 8 yield π-allyl 7 enolate 9, respectively. stereoselectivity also clarified according single-point calculations intermediates 9.

Language: Английский

Carbonyl umpolung as an organometallic reagent surrogate DOI
Xi‐Jie Dai, Chenchen Li, Chao‐Jun Li

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10733 - 10742

Published: Jan. 1, 2021

Carbonyls can serve as surrogates for organometallic reagents via hydrazones.

Language: Английский

Citations

78
Cooperative Ni/Cu‐Catalyzed Asymmetric Propargylic Alkylation of Aldimine Esters DOI
Lingzi Peng,

Zhuozhuo He,

Xianghong Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(34), P. 14270 - 14274

Published: May 18, 2020

A novel Ni/Cu dual catalysis gives rise to fundamentally new cooperative reactivity and enables the regio- enantioselective propargylic alkylation reaction. diverse set of α-quaternary propargylated amino ester derivatives were synthesized in good yields with excellent enantioselectivity (up 99 % ee). This work highlights power catalysis, which can be expected have broad implications homogeneous beyond highly valuable synthetic intermediates.

Language: Английский

Citations

76
Cobalt-Catalyzed Diastereo- and Enantioselective Reductive Allyl Additions to Aldehydes with Allylic Alcohol Derivatives via Allyl Radical Intermediates DOI
Lei Wang, Lifan Wang, Mingxia Li

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12755 - 12765

Published: Aug. 5, 2021

Catalytic generation of ambiphilic π-allyl–metal complexes and their utility in enantioselective transformations constitutes a powerful approach for introduction allyl groups to molecule. Herein an unprecedented cobalt-catalyzed highly site-, diastereo-, protocol stereoselective formation nucleophilic allyl–Co(II) followed by addition aldehydes is presented. The reaction features diastereo- enantioconvergent conversion easily accessible allylic alcohol derivatives diversified enantioenriched homoallylic alcohols with remarkably broad scope that can be introduced. Mechanistic studies indicated radical intermediates were involved this process. These new discoveries establish strategy development through capture radicals chiral Co complexes, pushing forward the frontier catalysis.

Language: Английский

Citations

68
Catalytic asymmetric C–C cross-couplings enabled by photoexcitation DOI
Giacomo E. M. Crisenza, Adriana Faraone, Eugenio Gandolfo

et al.

Nature Chemistry, Journal Year: 2021, Volume and Issue: 13(6), P. 575 - 580

Published: May 24, 2021

Language: Английский

Citations

66
Mechanistic Study of Ni and Cu Dual Catalyst for Asymmetric C–C Bond Formation; Asymmetric Coupling of 1,3-Dienes with C-nucleophiles to Construct Vicinal Stereocenters DOI

Jingzhao Xia,

Takahiro Hirai, Shoichiro Katayama

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6643 - 6655

Published: May 21, 2021

We report details of the reaction mechanism for a coupling 1,3-dienes with C-nucleophiles that was catalyzed by Ni/Cu cooperative catalyst system using Ni(cod)2 and [Cu(CH3CN)4]PF6 in presence chiral JOSIPHOS-type bisphosphine ligand iPr2NEt, providing direct access to highly valuable vicinal quaternary tertiary stereocenters high enantio- diastereoselectivity. The bimetallic exhibited broad substrate scope, including both cyclic/acyclic stabilized nucleophiles aryl-/alkyl-substituted 1,3-dienes. elucidated depth isolating characterizing four key complexes nickel copper conducting deuterium labeling experiments, kinetic studies, density functional theory calculations. turnover-limiting step this is proton-transfer diene-coordinated Ni complex 6 from cationic Cu 8 yield π-allyl 7 enolate 9, respectively. stereoselectivity also clarified according single-point calculations intermediates 9.

Language: Английский

Citations

65