Au(I) as a π‑Lewis Base Catalyst: Controlled Synthesis of Sterically Congested Bis(triflyl)enals from α‑Allenols

Toledano Pinedo, Mireia; Martínez Del Campo, Teresa; Yanai, Hikaru; Almendros, Pedro

Au(I) as a π‑Lewis Base Catalyst: Controlled Synthesis of Sterically Congested Bis(triflyl)enals from α‑Allenols

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2022 ACS Catalysis.pdf (2.97 MB)

Official URL

https://doi.org/10.1021/acscatal.2c03858

Publication date

2022

Authors

Toledano Pinedo, Mireia

Martínez Del Campo, Teresa

Yanai, Hikaru

Almendros, Pedro

Publisher

ACS Publications

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URI

https://hdl.handle.net/20.500.14352/104913

Citation

Mireia Toledano-Pinedo, Teresa Martínez del Campo, Hikaru Yanai, and Pedro Almendros ACS Catalysis 2022 12 (19), 11675-11681 DOI: 10.1021/acscatal.2c03858

Abstract

A gold-catalyzed bis[(trifluoromethyl)sulfonyl]ethylation of α-allenols, which allows the preparation of sterically congested bis(triflyl)enals bearing quaternary carbon centers, is presented. This sequence differs from the conventional reaction pathway of α-allenols under π-acid catalysis, because in our case Au(I) functions as a π-Lewis base catalyst rather than a π-Lewis acid to activate the allene, facilitating the unusual addition of a carbon nucleophile of the gold complex belonging to the allenol moiety. Density functional theory calculations were carried out to understand this uncommon pathway.