Palladium catalysis in intramolecular carbene C-H insertion of α-diazo-α-(methoxycarbonyl)acetamides to form β-lactams

The intramolecular carbene C-H insertion of α‐diazo‐α‐(methoxycarbonyl)acetamides leading to β‐lactams is effectively catalyzed by palladium complexes. It is found that although Pd0 catalysts typically produce mixtures of β‐lactams together with Buchner‐type reaction products, the use of PdII cataly...

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Detalhes bibliográficos
Autores: Solé Arjó, Daniel, Pérez Janer, Ferran, Bennasar Fèlix, M. Lluïsa, Fernández Cadenas, Israel
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Recursos:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/128153
Acesso em linha:https://hdl.handle.net/2445/128153
Access Level:acceso abierto
Palavra-chave:Pal·ladi (Element químic)
Catàlisi
Síntesi orgànica
Complexitat computacional
Palladium
Catalysis
Organic synthesis
Computational complexity
Descrição
Resumo:The intramolecular carbene C-H insertion of α‐diazo‐α‐(methoxycarbonyl)acetamides leading to β‐lactams is effectively catalyzed by palladium complexes. It is found that although Pd0 catalysts typically produce mixtures of β‐lactams together with Buchner‐type reaction products, the use of PdII catalysts results in highly chemoselective transformations. According to DFT calculations, this insertion reaction occurs stepwise and involves an unprecedented PdII‐promoted Mannich‐type reaction through a metallacarbene‐induced zwitterionic intermediate.