Stereospecific [2,3] sigmatropic rearrangement of allylic sulfoxides and selenoxides. Synthesis of novel polycyclic allylic alcohols and alpha-hydroxy ketones

A stereospecific [2,3] sigmatropic rearrangement of functionalized bi- or t ricyclic allylic sulfoxides and selenoxides as a route to new allylic alcoh ols and their transformation into the corresponding ol-hydroxy ketones havi ng a defined stereochemistry is described. It has been demonstrated that cy cloadducts, derived from [4+2] cycloaddition of (Z)-1-alkylthio-2-diethoxyp hosphoryloxy-1,3-dienes to a various dienophiles, are versatile synthons ca rrying much structural and stereochemical information. (C) 2001 Elsevier Sc ience Ltd. All rights reserved.