Highly Selective 1,3-Isomerization of Allylic Alcohols via Rhenium Oxo Catalysis

Abstract

Two reaction strategies are developed to promote the highly selective 1,3-isomerization of a variety of allylic alcohols using O_3ReOSiPh_3 as a catalyst. The first strategy utilizes substrates whose 1,3-regioisomer contains a conjugated alkene, which relies on thermodynamics to obtain high selectivity. The second strategy employs N,O-bis(trimethylsilyl)acetamide as an additive to selectively and irreversibly remove the product from the reaction equilibrium and works well for the isomerization of tertiary allylic alcohols into primary allylic alcohols containing trisubstituted alkene components. High stereoselectivity is also observed in the 1,3-isomerization of enantioenriched allylic alcohols.