Insights into the gold(I)-catalyzed intermolecular annulations of alkynes with N-allenamides: a mechanistic DFT study

Qing Sun; Tian-Yu Deng; Jia-Jie Chen; Jia-Yi Liu; Xin Lu; Zhi-Xia Zhang; Jin-Heng Li

doi:10.1039/d1dt04028f

Insights into the gold(I)-catalyzed intermolecular annulations of alkynes with N-allenamides: a mechanistic DFT study

Dalton Trans. 2022 Mar 1;51(9):3734-3739. doi: 10.1039/d1dt04028f.

Authors

Qing Sun¹, Tian-Yu Deng², Jia-Jie Chen¹, Jia-Yi Liu¹, Xin Lu³, Zhi-Xia Zhang¹, Jin-Heng Li^{1

4}

Affiliations

¹ Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063, China. sunqing@nchu.edu.cn.
² Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
³ State Key Laboratory of Physical Chemistry of Solid Surface & Fujian Provincial Key Laboratory for Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
⁴ School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 475004, China.

PMID: 35166737
DOI: 10.1039/d1dt04028f

Abstract

The mechanism of Au(I)-catalyzed intermolecular annulation of 2-(1-alkynyl)-2-alken-1-one with N-allenamide was carefully elucidated using density functional theory (DFT). The reaction is initiated by the binding of the Au(I) catalyst with 2-(1-alkynyl)-2-alken-1-one rather than with N-allenamide. The key intermediate, a gold all-carbon 1,3-dipole species, is revealed to be more reactive than the gold allylic carbocation. The influence of ligands and substituents was rationally analyzed. We believe that our study will provide deeper mechanistic insights into the chemoselective reactions of alkynes with N-allenamide.