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

Toledano Pinedo, MireiaMartínez Del Campo, TeresaYanai, HikaruAlmendros, Pedro2024-06-132024-06-132022-09-12Mireia Toledano-Pinedo, Teresa Martínez del Campo, Hikaru Yanai, and Pedro Almendros ACS Catalysis 2022 12 (19), 11675-11681 DOI: 10.1021/acscatal.2c0385810.1021/acscatal.2c03858https://hdl.handle.net/20.500.14352/104913A 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.engAttribution 4.0 InternationalAu(I) as a π‑Lewis Base Catalyst: Controlled Synthesis of Sterically Congested Bis(triflyl)enals from α‑Allenolsjournal articlehttps://doi.org/10.1021/acscatal.2c03858open access547allenesgold π-Lewis base catalystquaternary centerselectivityCiencias23 Química