Functional-Group-Tolerant, Silver-Catalyzed N−N Bond Formation by Nitrene Transfer to Amines

Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhINTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the c...

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Detalhes bibliográficos
Autores: Maestre, Lourdes, Dorel, Ruth, Pablo, Óscar, Escofet, Imma, Sameera, W. M. C., Álvarez, Eleuterio, Maseras, Feliu, Díaz-Requejo, M. Mar, Echavarren, Antonio M., Peŕez, Pedro J.
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/335521
Acesso em linha:http://hdl.handle.net/2072/335521
https://doi.org/10.1021/jacs.6b08219
Access Level:acceso abierto
Palavra-chave:54
Descrição
Resumo:Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhINTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C−H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N−N bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.