Interrogating the anti-Insertion of Alkynes into Gold(III) DOI Creative Commons
Jaime Martín, Johannes Schörgenhumer, Cristina Nevado

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(3), P. 1439 - 1447

Published: Feb. 26, 2025

Alkyne hydrofunctionalizations are a powerful strategy to efficiently build up structural complexity. The selectivity of these reactions is typically governed by the interaction between alkyne and metal-hydride, which commonly proceeds via well-understood syn-insertion mechanism. In contrast, anti-insertions far less common, with proposed mechanisms often extrapolated from literature precedents rather than grounded in direct experimental evidence. While gold complexes rank among most efficient catalysts for such transformations, mechanistic understanding key insertion step remains incomplete. this study, we demonstrate that stable gold(III)-hydrides, featuring (P∧N∧C) ligand, undergo selective alkynes yield corresponding anti-Markovnikov Z-vinyl complexes. A combination control experiments, kinetic studies, computational analyses reveals nonradical, bimolecular process, water plays pivotal role accelerating reaction potentially stabilizing highly reactive, T-shaped gold(I) intermediate. Notably, first demonstration both activated unactivated terminal internal into gold(III)-hydride complex.

Language: Английский

Interrogating the anti-Insertion of Alkynes into Gold(III) DOI Creative Commons
Jaime Martín, Johannes Schörgenhumer, Cristina Nevado

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(3), P. 1439 - 1447

Published: Feb. 26, 2025

Alkyne hydrofunctionalizations are a powerful strategy to efficiently build up structural complexity. The selectivity of these reactions is typically governed by the interaction between alkyne and metal-hydride, which commonly proceeds via well-understood syn-insertion mechanism. In contrast, anti-insertions far less common, with proposed mechanisms often extrapolated from literature precedents rather than grounded in direct experimental evidence. While gold complexes rank among most efficient catalysts for such transformations, mechanistic understanding key insertion step remains incomplete. this study, we demonstrate that stable gold(III)-hydrides, featuring (P∧N∧C) ligand, undergo selective alkynes yield corresponding anti-Markovnikov Z-vinyl complexes. A combination control experiments, kinetic studies, computational analyses reveals nonradical, bimolecular process, water plays pivotal role accelerating reaction potentially stabilizing highly reactive, T-shaped gold(I) intermediate. Notably, first demonstration both activated unactivated terminal internal into gold(III)-hydride complex.

Language: Английский

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