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

Journal of the Brazilian Chemical Society

Diego S. Pisoni²  Daniel B. Silva²  Rossana A. Schenato¹  Marco A. Ceschi² 

[1] ,Universidade Federal do Rio Grande do Sul Instituto de Química Porto Alegre RS ,Brazil

关键词: limonene oxide;    bicyclo[3.3.0]octane;    chiral;    building block;   

DOI  :  10.1590/S0103-50532004000500007

来源: SciELO

【 摘 要 】

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.

【 授权许可】

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