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Chinese Journal of Organic Chemistry >

2021 , Vol. 41 >Issue 11: 4347 - 4352

DOI: https://doi.org/10.6023/cjoc202107031

ARTICLES

Mechanistic Study of Cu-Catalyzed Addition Reaction of lsocyanates

  • Li Huang ,
  • Yuhao Wang ,
  • Jiying Liu ,
  • Shijun Li ,
  • Wenjing Zhang ,
  • Yu Lan
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  • 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
* Corresponding authors. E-mail:
;

Received date: 2021-07-15

  Revised date: 2021-08-15

  Online published: 2021-08-25

Supported by

National Natural Science Foundation of China(21903071); Program for Science Technology Innovation Talents in Universities of Henan Province(20HASTIT004)

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Abstract

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

Cite this article

Li Huang , Yuhao Wang , Jiying Liu , Shijun Li , Wenjing Zhang , Yu Lan . Mechanistic Study of Cu-Catalyzed Addition Reaction of lsocyanates[J]. Chinese Journal of Organic Chemistry, 2021 , 41(11) : 4347 -4352 . DOI: 10.6023/cjoc202107031

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