Stereoselective [3,3]-sigmatropic rearrangement promoted by the metal [1,3]-shift of binuclear Fischer carbene complexes.
Reaction of chiral homobinuclear Fischer chromium carbene complexes with allyl alcohol in the presence of NaH and the following oxidative demetalation gave alpha-allyl esters in up to 97% ee via [3,3]-sigmatropic rearrangement reaction promoted by the metal 1,3-shift. On the other hand, chiral heterobinuclear tungsten carbene complexes with arene chromium complexes afforded alpha-allyl-beta-hydroxy esters as a major product in up to 92/8 dr by the same reaction sequence.
Kamikawa
Ken
K
Department of Chemistry, Faculty of Integrated Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan.
Tachibana
Atsushi
A
Shimizu
Yasunori
Y
Uchida
Kazuya
K
Furusho
Masaru
M
Uemura
Motokazu
M