4.8 Article

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

期刊

ACS CATALYSIS
卷 11, 期 11, 页码 6643-6655

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c01626

关键词

asymmetric allylic alkylation; nickel; copper; dual catalyst; kinetics; DFT calculations

资金

  1. China Postdoctoral Science Foundation [2019M661478]
  2. JSPS KAKENHI [20K152770]
  3. National Key R&D Program of China [2018YFE0126800]
  4. National Natural Science Foundation of China [21831005]
  5. JSPS Research Fellowship for Young Scientists

向作者/读者索取更多资源

This study presents a comprehensive investigation of the reaction mechanism for a coupling reaction catalyzed by a Ni/Cu cooperative catalyst system, providing direct access to valuable stereocenters with high enantio- and diastereoselectivity. The mechanism of the bimetallic cooperative catalyst system was elucidated through isolation and characterization of key complexes, deuterium labeling experiments, kinetic studies, and density functional theory calculations. The turnover-limiting step involves a proton-transfer step between Ni and Cu complexes to yield the desired products with specific stereochemistry.
We report details of the reaction mechanism for a coupling reaction of 1,3-dienes with C-nucleophiles that was catalyzed by a Ni/Cu cooperative catalyst system using Ni(cod)(2) and [Cu(CH3CN)(4)]PF6 in the presence of a chiral JOSIPHOS-type bisphosphine ligand and (Pr2NEt)-Pr-i, providing direct access to highly valuable vicinal quaternary and tertiary stereocenters with high enantio- and diastereoselectivity. The bimetallic cooperative catalyst system exhibited a broad substrate scope, including both cyclic/acyclic stabilized nucleophiles and aryl-/alkyl-substituted 1,3-dienes. The bimetallic cooperative catalyst mechanism was elucidated in depth by isolating and characterizing four key complexes of nickel and copper and conducting deuterium labeling experiments, kinetic studies, and density functional theory calculations. The turnover-limiting step of this reaction is the proton-transfer step to diene-coordinated Ni complex 6 from cationic Cu complex 8 to yield p-allyl Ni complex 7 and Cu enolate complex 9, respectively. The stereoselectivity of the reaction was also clarified according to single-point calculations of the key intermediates 7 and 9.

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