Asymmetric dehydration of β-hydroxy esters and application to the syntheses of flavane derivatives

Catalytic asymmetric dehydration of β-aryl or alkyl substituted β-hydroxy esters via kinetic resolution has been investigated. A brief survey of 10 different chiral ligands is conducted to examine the effects of chiral ligand structure on selectivity of the dehydration. The kinetic resolution of a variety of rac-β-hydroxy tert-butyl esters in the presence of prolinol chiral ligand 2 and BrZnCH2CO2-t-Bu can provide highly enantioenriched β-hydroxy esters 14–21 with selectivity factors ranging from 11 to 66. Also, application of this asymmetric synthetic methodology to the preparation of enantioenriched flavane derivatives 25–29 is demonstrated.