Catalytic Carbocation Generation Enabled by the Mesolytic Cleavage of Alkoxyamine Radical Cations.
Angew Chem Int Ed Engl
; 55(34): 9969-73, 2016 08 16.
Article
en En
| MEDLINE
| ID: mdl-27403637
ABSTRACT
A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. In this process, electron transfer between an excited state oxidant and a TEMPO-derived alkoxyamine substrate gives rise to a radical cation with a remarkably weak C-O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO(.) as well as a reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles. Notably, this process occurs under neutral conditions and at comparatively mild potentials, enabling catalytic cation generation in the presence of both acid sensitive and easily oxidized nucleophilic partners.
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1
Bases de datos:
MEDLINE
Asunto principal:
Compuestos Organometálicos
/
Alcoholes
/
Aminas
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2016
Tipo del documento:
Article
País de afiliación:
Estados Unidos