Asymmetric synthesis of alpha-amino allyl, benzyl, and propargyl silanes by metalation and rearrangement.
[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.
Sieburth
Scott McN
SM
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA. sieburth@astro.temple.edu
O'Hare
Heather K
HK
Xu
Jiayi
J
Chen
Yanping
Y
Liu
Guodong
G
D000498:Allyl Compounds / Q000138:chemical synthesis*; D001593:Benzyl Compounds / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D003500:Cyclization; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D012821:Silanes / Q000138:chemical synthesis*
D000498:Allyl Compounds; D001593:Benzyl Compounds; D008670:Metals; D012821:Silanes; D010100:Oxygen