Intermolecular Allene Functionalization by Silver-Nitrene Catalysis

Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI═NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since ary...

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Detalhes bibliográficos
Autores: Ramírez Rodríguez, Manuel, Besora, María, Molina González, Francisco, Maseras, Feliu, Díaz Requejo, María Mar, Pérez Romero, Pedro José
Formato: artículo
Fecha de publicación:2020
País:España
Recursos:Universidad de Huelva (UHU)
Repositorio:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Idioma:inglés
OAI Identifier:oai:ariasmontano.uhu.es:10272/19650
Acesso em linha:http://hdl.handle.net/10272/19650
Access Level:acceso abierto
Palavra-chave:Allene aziridination
Allene C-N bond formation
Intermolecular nitrene transfer
Silver catalysis
Aminocyclopropanes
Methylene aziridines
23 Química
Descrição
Resumo:Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI═NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since arylallenes are converted into azetidine derivatives, whereas methylene aziridines are the products resulting from alkylallenes. Mechanistic studies allow proposing that azetidines are formed through unstable cyclopropylimine intermediates, which further incorporate a second nitrene group, both processes being silver-mediated. Methylene aziridines from alkylallenes derive from catalytic nitrene addition to the allene double bonds. Both routes have resulted to be productive for further synthetic transformations affording aminocyclopropanes.