Recent developments of direct rhenium-catalyzed [1,3]-transpositions of allylic alcohols and their silyl ethers.
The direct metal-catalyzed [1,3]-transposition of allylic alcohols and allylic silyl ethers is a synthetically useful isomerization process that occurs via [3,3]-sigmatropic rearrangement induced by high oxidation state oxometal complexes. The isomerization requires only a catalytic amount of promoter, and high chirality transfer can be achieved. Thus, it bears a significant potential to become a powerful tool in multistep synthesis. Although [1,3]-transposition of allylic alcohols has been known since the late 1960s, the development of synthetically useful protocols that allow for a high level of regio- and stereoselectivity control and their synthetic applications have emerged only recently. This tutorial review summarizes recently developed regioselective [1,3]-transpositions of allylic alcohols and silyl ethers and their applications to natural product synthesis.
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607, USA. dsunglee@uic.edu.
Ivan
I
Volchkov
Daesung
D
Lee