RT Journal Article T1 Au(I) as a π‑Lewis Base Catalyst: Controlled Synthesis of Sterically Congested Bis(triflyl)enals from α‑Allenols A1 Toledano Pinedo, Mireia A1 Martínez Del Campo, Teresa A1 Yanai, Hikaru A1 Almendros, Pedro AB 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. PB ACS Publications YR 2022 FD 2022-09-12 LK https://hdl.handle.net/20.500.14352/104913 UL https://hdl.handle.net/20.500.14352/104913 LA eng NO Mireia Toledano-Pinedo, Teresa Martínez del Campo, Hikaru Yanai, and Pedro Almendros ACS Catalysis 2022 12 (19), 11675-11681 DOI: 10.1021/acscatal.2c03858 DS Docta Complutense RD 26 jul 2024