Sieburth Scott McN, O'Hare Heather K, Xu Jiayi, Chen Yanping, Liu Guodong
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
Org Lett. 2003 May 29;5(11):1859-61. doi: 10.1021/ol034397y.
[reaction: see text] Metalation of a Boc-protected N-silylamine alpha to nitrogen results in migration of the silicon from nitrogen to carbon (reverse aza-Brook rearrangement), yielding an alpha-amino silane. The Boc group acts initially as a metalation-directing group and then to stabilize the nitrogen anion, providing a driving force for the rearrangement. In the presence of (-)-sparteine, the new chiral center is formed in >90% ee from allyl, benzyl, and propargylamines.
