Enantio- and Diastereoselective Nucleophilic Addition of N-tert-Butylhydrazones to Isoquinolinium Ions through Anion-Binding Catalysis

A highly enantio- and diastereoselective thiourea-catalyzed dearomatization of isoquinolines employing N-tert-butylhydrazones as neutral α-azo carbanions and masked acyl anion equivalents has been developed. Experimental and computational data supports the generation of highly ordered complexes wher...

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Detalhes bibliográficos
Autores: Matador Martínez, Esteban, Iglesias Sigüenza, Francisco Javier, Monge Fernández, David, Merino, Pedro, Fernández Fernández, Rosario Fátima, Lassaletta, José M.
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2021
País:España
Recursos:Universidad de Sevilla (US)
Repositório:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/139856
Acesso em linha:https://hdl.handle.net/11441/139856
https://doi.org/10.1002/anie.202012861
Access Level:Acceso aberto
Palavra-chave:Acylation
Asymmetric catalysis
Dearomatization
Hydrazones
Organocatalysis
Descrição
Resumo:A highly enantio- and diastereoselective thiourea-catalyzed dearomatization of isoquinolines employing N-tert-butylhydrazones as neutral α-azo carbanions and masked acyl anion equivalents has been developed. Experimental and computational data supports the generation of highly ordered complexes wherein the chloride behaves as a template for the catalyst, the hydrazone reagent, and the isoquinolinium cation, providing excellent stereocontrol in the formation of two contiguous stereogenic centers. The ensuing selective and high-yielding transformations provide appealing dihydroisoquinoline derivatives.