INTRAMOLECULAR CYCLOPROPANATION-RING FRAGMENTATION LEADING TO SPIROCYCLIC RING CONSTRUCTION - A STEREOSELECTIVE SYNTHESIS OF BETA-CHAMIGRENE

被引：17

作者：

ADAMS, J ^{[1
]}

LEPINEFRENETTE, C ^{[1
]}

SPERO, DM ^{[1
]}

机构：

[1] BIO MEGA INC,LAVAL H7S 2G7,QUEBEC,CANADA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 14期

关键词：

D O I：

10.1021/jo00014a032

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The transannular cyclopropanation of a keto carbene generated by Rh2(OAc)4 catalysis on a bicyclic dihydropyran nucleus provided a key oxatricyclic ketone intermediate for the synthesis of the [6.6] spirocyclic ring construction. Selective fragmentation of the cyclopropane followed by hydrolytic cleavage of the C-O bond provided the spirocyclic skeleton. Functional group manipulations to adjust oxidation states led to a total synthesis of (+/-)-beta-chamigrene in 14 steps without the use of protection/deprotection schemes.

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页码：4494 / 4498

页数：5

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