In the reaction of higher order cyanocuprates with N,O-bis(trimethylsily1)hydroxylamine delivery of the NHSiMes moiety to one of the anionic ligands in the cuprate takes place even in the absence of external bases according to an "electrophilic amination" protocol. Details of the methodology are given, and the reaction mechanism is analyzed in terms of interception by a mixed bis-metal cluster of a lithium N-silyl-N-siloxyamide, followed by intramolecular C-N coupling. This method is applicable to cyanocuprates bearing aromatic, heteroaromatic, and saturated aliphatic ligands. A number of 2-amino-substituted heterocycles, not easily accessible by normal routes, can be obtained with the aid of a stabilizing silylation at the nitrogen atom
Electrophilic amination of higher order cuprates with N,O-Bis-(trimethylsiyl)hydroxylamine
Reginato Gianna;Seconi Giancarlo
1993
Abstract
In the reaction of higher order cyanocuprates with N,O-bis(trimethylsily1)hydroxylamine delivery of the NHSiMes moiety to one of the anionic ligands in the cuprate takes place even in the absence of external bases according to an "electrophilic amination" protocol. Details of the methodology are given, and the reaction mechanism is analyzed in terms of interception by a mixed bis-metal cluster of a lithium N-silyl-N-siloxyamide, followed by intramolecular C-N coupling. This method is applicable to cyanocuprates bearing aromatic, heteroaromatic, and saturated aliphatic ligands. A number of 2-amino-substituted heterocycles, not easily accessible by normal routes, can be obtained with the aid of a stabilizing silylation at the nitrogen atomI documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.