Synthesis of protected chiral vicinal diaminoalcohols by diastereoselective intramolecular benzylic substitution from bistrichloroacetimidates.
An efficient synthesis of chiral dihydrooxazines (2) from 1-aryl-2-amino-propane-1,3-diols (1) via the corresponding bistrichloroacetimidate intermediates has been developed. In this transformation, one trichloroacetimidate acts as a leaving group and the other acts as a nucleophile. The cyclization proceeds through an SN1 mechanism to provide trans-dihydrooxazines with complete diastereoselectivity irrespective of the absolute configuration of the benzylic alcohol. The transformation of 2 into other selectively protected aminodiols is also documented. [reaction: see text].
Rondot
Christophe
C
Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France.
Retailleau
Pascal
P
Zhu
Jieping
J
D000605:Amino Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D062845:Chloroacetates; D018360:Crystallography, X-Ray; D003500:Cyclization; D007094:Imides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D015394:Molecular Structure; D012680:Sensitivity and Specificity; D013237:Stereoisomerism; D014238:Trichloroacetic Acid / Q000737:chemistry*
D000605:Amino Alcohols; D062845:Chloroacetates; D007094:Imides; D014238:Trichloroacetic Acid