Stereoselective 3,3-Sigmatropic Rearrangement Utilizing Binuclear alpha,beta-Unsaturated Fischer Carbene Complexes with Planar Chiral (Arene)chromium Complex

摘要

Optically enriched binuclear alpha,beta-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes were utilized for Stereoselective [3,3]-sigmatropic rearrangement reaction. Reaction of chiral homo-binuclear Fischer chromium carbene complexes with allyl alcohol in the presence of NaH and the following oxidative demetallation gave alpha-allyl esters up to 97 %ee via [3,3]-sigmatropic rearrangement reaction promoted by the metal 1,3-shift. On the other hand,hetero-binuclear tungsten carbene complexes with arene chromium complexes afforded alpha-allyl-beta-hydroxy esters as a major product up to 92/8 dr.