Enantioselective synthesis of a-aryl a-hydrazino phosphonates

Catalysts generated in situ by the combination of pyridine–hydrazone N,N-ligands and Pd(TFA)2 have been applied to the addition of arylboronic acids to formylphosphonate-derived hydrazones, yielding α-aryl α-hydrazino phosphonates in excellent enantioselectivities (96 → 99% ee). Subsequent removal o...

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Detalhes bibliográficos
Autores: Alberca, Saúl, Romero Parra, Javier, Fernández López, Israel, Fernández, Rosario, Lassaletta, José M., Monge, David
Formato: artículo
Fecha de publicación:2024
País:España
Recursos:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/108997
Acesso em linha:https://hdl.handle.net/20.500.14352/108997
Access Level:acceso abierto
Palavra-chave:547
Química orgánica (Química)
2306 Química Orgánica
Descrição
Resumo:Catalysts generated in situ by the combination of pyridine–hydrazone N,N-ligands and Pd(TFA)2 have been applied to the addition of arylboronic acids to formylphosphonate-derived hydrazones, yielding α-aryl α-hydrazino phosphonates in excellent enantioselectivities (96 → 99% ee). Subsequent removal of the benzyloxycarbonyl (Cbz) N-protecting group afforded key building blocks en route to appealing artificial peptides, herbicides and antitumoral derivatives. Experimental and computational data support a stereochemical model based on aryl-palladium intermediates in which the phosphono hydrazone coordinates in its Z-configuration, maximizing the interactions between the substrate and the pyridine–hydrazone ligand.