The case for noncompetitive cyclizative options during attempted expedient construction of the core ring system of CP-263,114

Abstract

The C-6 alkylation of 2-cyclohexenone with methyl bromoacetate was followed by brominationdehydrobromination of the double bond. Palladium-catalyzed coupling of 8 to dimethyl (E)-2-hexenedioate provided the key triester 4. All attempts to bring about intramolecular oxidative cyclization of the dienolate of 4 was found to result in preferred formation of the Dieckmann product 9 instead.