Copper-Catalyzed Enantioselective Borylative Allyl–Allyl Coupling of Allenes and Allylic gem-Dichlorides

A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem-dichloride and provides chiral internal 1,5-dienes featuring (Z)-configured alkeny...

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Detalles Bibliográficos
Autores: Piñeiro-Suárez, Martín, Álvarez-Constantino, Andrés M., Fañanás-Mastral, Martín
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad de Santiago de Compostela (USC)
Repositorio:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Idioma:inglés
OAI Identifier:oai:minerva.usc.gal:10347/31152
Acceso en línea:http://hdl.handle.net/10347/31152
Access Level:acceso abierto
Descripción
Sumario:A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem-dichloride and provides chiral internal 1,5-dienes featuring (Z)-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate–ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the (Z)-alkenyl chloride