Nazarov cyclization of divinyl ketones bearing an ester group at the β-position: a remarkable effect of α-substitution and alkene geometry on regioselectivity

Abstract

The Nazarov cyclization of divinyl ketones with an ester at the β-position was examined with particular reference to where the cyclic double bond forms. We observed unprecedented regioselectivity, dictated by the subtle substitution patterns at the α-position and alkene geometry of α,β and mostly, this selectivity is regardless of substitutions at α′- and β′-positions. The major implications of these observations are an aromatic group at the α-position with E-olefin geometry provides a cyclopentenone in which the double bond is not in conjugation with an ester, whereas Z-olefin provides a cyclopentenone in which the double bond is in conjugation with an ester; and divinyl ketones bearing an ester group at the β-position and an alkyl group at the α-position with E-olefin geometry provide a cyclopentenone in which the double bond is in conjugation with the ester.