Understanding the reaction mechanism of anti-addition of (NHC)Au(i)–H and (NHC)Au(i)–F across alkyne

Abstract

The experimentally observed anti-addition reactions of (NHC)Au(I)–H with dimethyl acetylenedicarboxylate (DMAD) MeOOCC[triple bond, length as m-dash]CCOOMe and (NHC)Au(I)–F with phenylacetylene MeC[triple bond, length as m-dash]CPh are intriguing and deserve more in-depth study. In this work, with the aid of density functional theory (DFT) calculations and intrinsic bond orbital (IBO) analysis, we systematically investigated the addition reactions of (NHC)Au(I)–X (X = H, Me and halides) with different alkynes. We found that the nature of the two anti-addition reactions is different. The addition of (NHC)Au(I)–H is initiated by a direct nucleophilic hydride attack from (NHC)Au(I)–H, followed by migration of the [(NHC)Au(I)]+ moiety to the diagonally opposite side with the aid of the out-of-plane π-bond of the alkyne. However, in the addition of (NHC)Au(I)–F, the [(NHC)Au(I)]+ moiety functions as a Lewis acid to initially activate the alkyne, followed by the fluoride attack.

Graphical abstract: Understanding the reaction mechanism of anti-addition of (NHC)Au(i)–H and (NHC)Au(i)–F across alkyne

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Article information

Article type
Research Article
Submitted
04 Mar 2025
Accepted
20 Mar 2025
First published
21 Mar 2025
This article is Open Access
Creative Commons BY-NC license

Org. Chem. Front., 2025, Advance Article

Understanding the reaction mechanism of anti-addition of (NHC)Au(I)–H and (NHC)Au(I)–F across alkyne

W. C. Chan and Z. Lin, Org. Chem. Front., 2025, Advance Article , DOI: 10.1039/D5QO00432B

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