Highly Stereoselective Synthesis and Hydrogenation of (Z)‑1-Alkyl-2- arylvinyl Acetates: a Wide Scope Procedure for the Preparation of Chiral Homobenzylic Esters

A synthesis of (Z)-1-alkyl-2-arylvinyl acetates 3 with broad scope is reported by using two complementary methods. The first one uses a stereospecific gold-catalyzed addition of acetic acid to 1-iodo-alkynes, followed by a Suzuki coupling. By the second, 1-methyl-2-arylvinyl substrates have been obt...

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Detalhes bibliográficos
Autores: González-Liste, Pedro J., León, Félix, Arribas, Inmaculada, Rubio Moreno, Miguel, García-Garrido, Sergio E., Cadierno, Victorio, Pizzano, Antonio
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2016
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/133408
Acesso em linha:http://hdl.handle.net/10261/133408
Access Level:acceso abierto
Palavra-chave:Iodo-alkenes
Enol esters
Asymmetric hydrogenation
Chiral esters
Rh catalysts
Descrição
Resumo:A synthesis of (Z)-1-alkyl-2-arylvinyl acetates 3 with broad scope is reported by using two complementary methods. The first one uses a stereospecific gold-catalyzed addition of acetic acid to 1-iodo-alkynes, followed by a Suzuki coupling. By the second, 1-methyl-2-arylvinyl substrates have been obtained selectively as the Z isomers by O-acylation of enolates of methyl benzyl ketones. In addition, the asymmetric hydrogenation of enol esters 3 has been covered for the first time. Using rhodium catalysts based on chiral phosphinephosphite ligands (P-OP), highly enantioselective hydrogenations (up to 99% ee) have been achieved for a wide range of substrates. Thus, the synthesis and enantioselective hydrogenation of 3 provides a convenient and versatile procedure for the synthesis of valuable chiral homobenzylic esters