Double diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Stephen G Davies; A Christopher Garner; Rebecca L Nicholson; James Osborne; Edward D Savory; Andrew D Smith

doi:10.1039/b306323m

Double diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Chem Commun (Camb). 2003 Sep 7:(17):2134-5. doi: 10.1039/b306323m.

Authors

Stephen G Davies¹, A Christopher Garner, Rebecca L Nicholson, James Osborne, Edward D Savory, Andrew D Smith

Affiliation

¹ The Dyson Perrins Laboratory, University of Oxford, South Parks Road, Oxford, UK OX1 3QY. steve.davies@chemistry.ox.ac.uk

PMID: 13678167
DOI: 10.1039/b306323m

Abstract

Asymmetric [3,3]-sigmatropic aza-Claisen rearrangement of the (Z)-N-allyl-N,O-silylketene aminal of (3S,4E,alphaR)-1-benzyloxy-3-(N-propionyl-N-alpha-methylbenzylamino)hex-4-ene furnishes (2S,3R,4E,alphaR)-N-alpha-methylbenzyl-2,3-dimethyl-7-benzyloxyhept-4-enamide in > 92% d.e.; rearrangement of the diastereomeric (3R,4E,alphaR)-(Z)-N,O-silylketene aminal proceeds with low diastereoselectivity.