Enantioselective Folding of Enynes by Gold(I) Catalysts with a Remote C2-Chiral Element

Chiral gold(I) catalysts have been designed based on a modi-fied JohnPhos ligand with a distal C2-2,5-diarylpyrrolidine that creates a tight binding cavity. The C2-chiral element is close to where the C-C bond formation takes place in cycliza-tions of 1,6-enynes. These chiral mononuclear catalysts h...

Descripción completa

Detalles Bibliográficos
Autores: Zuccarello, Giuseppe, Mayans, Joan G., Escofet, Imma, Scharnagel, Dagmar, Kirillova, Mariia S., Pérez-Jimeno, Alba H., Calleja, Pilar, Boothe, Jordan R., Echavarren, Antonio M.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/522470
Acceso en línea:http://hdl.handle.net/2072/522470
https://doi.org/10.1021/jacs.9b06326
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:Chiral gold(I) catalysts have been designed based on a modi-fied JohnPhos ligand with a distal C2-2,5-diarylpyrrolidine that creates a tight binding cavity. The C2-chiral element is close to where the C-C bond formation takes place in cycliza-tions of 1,6-enynes. These chiral mononuclear catalysts have been applied for the enantioselective 5-exo-dig and 6-endo-dig cyclization of different 1,6-enynes as well as in the first enan-tioselective total synthesis of three members of the carexane family of natural products. Opposite enantioselectivities have been achieved in seemingly analogous reactions of 1,6-enynes, which result from different chiral folding of the substrates based on attractive aryl-aryl interactions.