Diastereoselective Osmium-catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives

Abstract

The osmium-catalyzed oxyamination of chiral acyclic allylic alcohol derivatives bearing mono- and 1,1-di-substituted double bonds with benzyl N-(4-tosyloxy)carbamate proceeds with high regioselectivity and moderate levels of diastereoselectivity favoring the anti product. The observed stereoselectivity shows a clear and systematic trend with anti:syn ratios increasing in line with the size of substituent at both the allylic stereocenter and double bond alpha-carbon. The stereoinduction is in accord with the sense of diastereoselectivity predicted by Kishi’s empirical rule and a previously reported transition state model for the osmium-catalyzed dihydroxylation of allylic alcohol derivatives. In contrast, allylic alcohol derivatives bearing trisubstituted double bonds show low or no reactivity in the oxyamination reaction affording the syn product in low yield in the cases examined.