Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (11): 4347-4352.DOI: 10.6023/cjoc202107031 Previous Articles     Next Articles

Special Issue: 热点论文虚拟合集

ARTICLES

铜催化异氰酸酯加成反应机理研究

黄利a, 王毓浩a, 刘吉英a, 李世俊a,*(), 张文静a,*(), 蓝宇a,b,*()   

  1. a 郑州大学化学学院 绿色催化中心 郑州 450001
    b 重庆大学化学化工学院 理论与计算化学重庆市重点实验室 重庆 400001
  • 收稿日期:2021-07-15 修回日期:2021-08-15 发布日期:2021-08-24
  • 通讯作者: 李世俊, 张文静, 蓝宇
  • 基金资助:
    国家自然科学基金(21903071); 河南省高校科技创新人才支持计划(20HASTIT004)

Mechanistic Study of Cu-Catalyzed Addition Reaction of lsocyanates

Li Huanga, Yuhao Wanga, Jiying Liua, Shijun Lia(), Wenjing Zhanga(), Yu Lana,b()   

  1. a Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001
    b Chongqing Key Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400001
  • Received:2021-07-15 Revised:2021-08-15 Published:2021-08-24
  • Contact: Shijun Li, Wenjing Zhang, Yu Lan
  • Supported by:
    National Natural Science Foundation of China(21903071); Program for Science Technology Innovation Talents in Universities of Henan Province(20HASTIT004)

As a C1 synthetic block, isocyanates were widely used in the synthesis of amide derivatives or heterocyclic compounds. Density functional theory (DFT) calculation was employed to reveal the mechanism of Cu(I)-catalyzed hydroboraethylation of isocyanates. Cu(I)OtBu was considered as the active species in catalytic cycle. The catalytic cycle involves transmetallation with borane, alkene insertion, isocyanate insertion, and transmetallation with LiOtBu to yield lithium acetylamide product. The isocyanate insertion was considered as rate-determining step, which underwent a unique three- membered ring type transition state. The catalytic cycle with chiral phosphine ligand was also considered for this reaction. DFT calculation resulted that the enantioselectivity was determined at the alkene insertion step, which was controlled by steric effect of phosphine ligand. Moreover, it was also found that the activation free energy for the rate-determining step with phosphine ligand was lower than that with carbene ligand. Therefore, the phosphine ligand would lead to a higher reaction rate.

Key words: cuprous catalysis, density functional theory (DFT) study, isocyanate, insertion