UNEXPECTED REARRANGEMENT IN THE PEROXYTRIFLUOROACETIC ACID-MEDIATED BAEYER-VILLIGER OXIDATION OF TRANS-3-BETA-HYDROXY-4,4,10-BETA-TRIMETHYL-9-DECALONE FORMING A 7-OXABICYCLO[2.2.1]HEPTANE - STRUCTURE PROOF AND TOTAL SYNTHESIS OF (+/-)-FARNESIFEROL-C

被引：24

作者：

DEMNITZ, FWJ ^{[1
]}

PHILIPPINI, C ^{[1
]}

RAPHAEL, RA ^{[1
]}

机构：

[1] UNIV CAMBRIDGE,CHEM LAB,CAMBRIDGE CB2 1EW,ENGLAND

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 16期

关键词：

D O I：

10.1021/jo00121a032

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A rearrangement in the Baeyer-Villiger oxidation of trans- 3 beta-hydroxy-4,4,10 beta-trimethyl-9-decalone (2a) and of OCH(2)OMe (2b) and OTHP (2c) derivatives using peroxytrifluoroacetic acid is reported. The reaction involves trifluoroacetic acid catalyzed rearrangement-of the initially formed hydroxy lactone 5a giving the 7-oxabicyclo[2.2.1]heptane carboxylic acid 6. This unexpected rearrangement is a useful preparation of the 7-oxabicyclo[2.2.1]heptane ring system and constitutes a stereoselective synthesis of the left-hand portion of the sesquiterpene-coumarin ether (+/-)-farnesiferol-C (10). The product 6 serves as an advanced, key intermediate from which a total synthesis and structure proof of this natural product is presented.

引用

页码：5114 / 5120

页数：7

共 41 条

[1] PHOSPHORUS TRIBROMIDE PROMOTED ALLYLIC REARRANGEMENT OF A TERTIARY VINYL CARBINOL - STEREOCHEMISTRY OF REACTION-PRODUCT AND APPLICATION TO SYNTHESIS OF JH-25, A POTENT JUVENILE-HORMONE MIMIC [J].