Computational Study of Silver-catalyzed Stereoselective Hydroalkylation of Alkynes: Pauli Repulsion Controlled / Selectivity

Overview

Journal Chem Commun (Camb)

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 4

PMID 34086023

Citations 6

Authors

Lingfei Hu

Han Gao

Yanlei Hu

Xiangying Lv

Yan-Bo Wu

Gang Lu

Affiliations

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Abstract

The mechanism and origin of stereoselectivity of silver-catalyzed hydroalkylation of alkynes were computationally investigated at the B3LYP-D3BJ/6-311+G(d,p)-SDD//B3LYP/6-31G(d)-LANL2DZ level. The complex of alkynyl trialkylboronate with cationic silver is a key intermediate, which triggers the rate- and stereoselectivity-determining 1,2-migration step. Energy decomposition analysis indicates that the difference of Pauli repulsion dominates the stereoselectivity.

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