Stereoselective isomerisation of N-allyl aziridines into geometrically stable Z enamines by using rhodium hydride catalysis.
Chemistry
; 14(3): 886-94, 2008.
Article
en En
| MEDLINE
| ID: mdl-17992683
ABSTRACT
In the presence of rhodium(I) hydride catalysts, tertiary N-allylamines are known to isomerise into E enamines. In contrast, we have recently found that N-allylaziridines isomerise to form Z enamines. On the basis of literature data, the most likely mechanism of isomerisation would involve a rhodium hydride addition/beta-hydride elimination sequence. We show that the observed selectivity cannot be adequately explained by this pathway and is more consistent with initial CH-activation followed by rearrangement to form a five-membered cyclometallated rhodium intermediate. This intermediate subsequently undergoes reductive elimination to form a C--H bond. The resulting geometrically stable Z enamines are useful building blocks for stereoselective synthesis.
Search on Google
Banco de datos:
MEDLINE
Asunto principal:
Rodio
/
Aziridinas
/
Aminas
Idioma:
En
Año:
2008
Tipo del documento:
Article