Models for Stereoselective Additions to Chiral Allylic Ethers: Osmium Tetroxide Bis-hydroxylations

Abstract

Density functional calculations (Becke3LYP/6-31G(d)) on the (3 + 2) transition structures of osmium tetroxide mediated dihydroxylations of chiral allylic ethers show that the stereoselectivity is controlled by the “inside alkoxy effect” (Stork/Houk-Jäger model). In the special case of Z-disubstituted alkenes, 1,3-allylic strain (Kishi model) controls the stereoselectivity.