A crystallographic study related to intramolecular hydride shifts in polycyclic hydroxyketones

Abstract

The crystal structures of the p-nitrobenzoate (p-NB) esters of the hydroxyketones (1)–(3) have been determined. These contain imbedded boat-conformation 4-hydroxycyclohexanones whose C(1)–C(4) distances decrease from 2.67(3)Å in (1)(R =p-NB) to 2.479(6)Å in (3)(R =p-NB). The relationship of the structural variation to the barriers and reaction path for the 1,4-hydride transfer in the corresponding alkoxide anions is discussed.