Au(I) as a π‑Lewis Base Catalyst: Controlled Synthesis of Sterically Congested Bis(triflyl)enals from α‑Allenols
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...
| Autores: | , , , |
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| Tipo de documento: | artigo |
| Data de publicação: | 2022 |
| País: | España |
| Recursos: | Universidad Complutense de Madrid (UCM) |
| Repositório: | Docta Complutense |
| Idioma: | inglês |
| OAI Identifier: | oai:docta.ucm.es:20.500.14352/104913 |
| Acesso em linha: | https://hdl.handle.net/20.500.14352/104913 |
| Access Level: | Acceso aberto |
| Palavra-chave: | 547 allenes gold π-Lewis base catalyst quaternary center selectivity Ciencias 23 Química |
| Resumo: | 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. |
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