Stereoselective E-carbofunctionalization of alkynes to vinyl-triflates via gold redox catalysis

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Campagnolo, Filippo, Armando, Lorenza, Boccalon, Elisa, Cicolella, Alessandra, Bochmann, Manfred, Talarico, Giovanni and Rocchigiani, Luca (2025) Stereoselective E-carbofunctionalization of alkynes to vinyl-triflates via gold redox catalysis. ACS Organic & Inorganic Au. ISSN 2694-247X

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Abstract

Carbofunctionalization of alkynes with trifluoromethylsulfonate nucleophiles is a powerful strategy for the synthesis of vinyl triflates with diverse molecular complexity. However, stereoselective protocols are challenging to realize, and the development of novel strategies for controlling the selectivity is highly desirable. In this work, we show that gold complexes bearing the hemilabile MeDalPhos ligand (MeDalPhos = di(1-adamantyl)-2-dimethylamino-phenylphosphine) catalyze the E-stereoselective carbofunctionalization of internal alkynes using aryl/vinyl iodides and AgOTf as simple starting reagents. Based on the outer-sphere nature of this reaction and the beneficial effect of the MeDalPhos ligand, the Z-selective attack is practically suppressed, leading to an ideal kinetic selectivity. Mechanistic studies, both experimental and theoretical, revealed that the interplay between kinetics and thermodynamics is crucial in determining the final E/Z ratios for each substrate.

Item Type: Article
Additional Information: Funding information: L.R. acknowledges the financial support from the Royal Society of Chemistry (R22-0875640255), the European Union─Next Generation EU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem grant ECS00000041─VITALITY. L.R. and G.T. also thank the European Union─Next Generation EU Missione 4, Componente 1 CUP J53D23007390001. M.B. thanks the Leverhulme Trust for an Emeritus Fellowship (EM-2024-0238\4).
Faculty \ School: Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
Depositing User: LivePure Connector
Date Deposited: 24 Sep 2025 15:30
Last Modified: 30 Sep 2025 16:30
URI: https://ueaeprints.uea.ac.uk/id/eprint/100463
DOI: 10.1021/acsorginorgau.5c00084

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