Preparation of (5R)-4,8-dimethylbicyclo[3.3.0]oct-1(8),3-dien-2-one from (-)-limonene oxide. A novel intermediate to the synthesis of 4-5-5 fused tricarbocyclic core present in terpenic natural products

Abstract

This paper describes the conversion of the readily available (-)-limonene oxide to the new (5R)-4,8-dimethylbicyclo[3.3.0]oct-1(8),3-dien-2-one. This compound holds the prospect of serving as a useful chiral building block or intermediate to prepare a variety of compounds having a bicyclo[3.3.0]octane framework. The synthetic strategy made use of the umpolung reactivity of cyanohydrin TMS ether, as an acyl anion equivalent, in order to promote intramolecular alkylation. The formal synthesis of (-)-kelsoene was achieved by preparing a known advanced intermediate (1R,5S,8R)-4,8-dimethylbicyclo[3.3.0] oct-3-en-2-one via selective hydrogenation of the named compound (5R)-4,8-dimethylbicyclo[3.3.0]oct-1(8),3-dien-2-one.