UNEXPECTED REARRANGEMENT IN THE PEROXYTRIFLUOROACETIC ACID-MEDIATED BAEYER-VILLIGER OXIDATION OF NS-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/

Authors
DEMNITZ FWJ PHILIPPINI C RAPHAEL RA
Citation
Fwj. Demnitz et al., UNEXPECTED REARRANGEMENT IN THE PEROXYTRIFLUOROACETIC ACID-MEDIATED BAEYER-VILLIGER OXIDATION OF NS-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/, Journal of organic chemistry, 60(16), 1995, pp. 5114-5120
Citations number
41
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Journal of organic chemistry → ACNP
ISSN journal
00223263
Volume
60
Issue
16
Year of publication
1995
Pages
5114 - 5120
Database
ISI
SICI code
0022-3263(1995)60:16<5114:URITPA>2.0.ZU;2-A
Abstract
A rearrangement in the Baeyer-Villiger oxidation of trans- 3 beta-hydr oxy-4,4,10 beta-trimethyl-9-decalone (2a) and of OCH(2)OMe (2b) and OT HP (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]hept ane carboxylic acid 6. This unexpected rearrangement is a useful prepa ration of the 7-oxabicyclo[2.2.1]heptane ring system and constitutes a stereoselective synthesis of the left-hand portion of the sesquiterpe ne-coumarin ether (+/-)-farnesiferol-C (10). The product 6 serves as a n advanced, key intermediate from which a total synthesis and structur e proof of this natural product is presented.