NOVEL AND EFFICIENT SYNTHESIS OF ROTENOIDS VIA INTRAMOLECULAR RADICAL ARYLATION

被引：24
作者：
AHMADJUNAN, SA [1 ]
AMOS, PC [1 ]
WHITING, DA [1 ]
机构：
[1] UNIV NOTTINGHAM, DEPT CHEM, NOTTINGHAM NG7 2RD, ENGLAND
来源：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1992年 / 05期
关键词：
D O I：
10.1039/p19920000539
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Treatment of the iodoarylchromenes 22 with palladium acetate gave the tetracyclic compounds 23 via a formal but stereochemically disallowed Heck reaction; a crystalline intermediate palladium species 25 (X-ray analysis) was isolated. The method was employed to synthesise the natural rotenoid (+/-)-munduserone 29. Related reductive radical cyclisation of enol acetate 31 gave the (+/-)-6a-alpha,12-alpha,12a-alpha-chromenochromenol acetate 32 (R = Ac), representing the core structure of the insecticidal rotenoid 2, in a 5 step (15% overall) route from 2-methylthiomethylchromone 17. The cis,cis-geometry is obtained stereospecifically through an intramolecular 6-exo addition mode.
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页码：539 / 545
页数：7
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