Acyclic Stereoselection in the Ortho Ester Claisen Rearrangement

The ortho ester Claisen rearrangement of trisubstituted allylic alcohols exhibits significant levels of diastereoselection. In E allylic alcohols, a 1,3-diaxial interaction develops in the chairlike transition state leading to the anti isomer, rendering the reaction syn selective by a factor of 3−5...

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Published inJournal of organic chemistry Vol. 62; no. 7; pp. 1976 - 1985
Main Authors Daub, G. William, Edwards, James P, Okada, Carol R, Allen, Jana Westran, Maxey, Claudia Tata, Wells, Matthew S, Goldstein, Alexandra S, Dibley, Michael J, Wang, Clarence J, Ostercamp, Daniel P, Chung, Steven, Cunningham, Paula Shanklin, Berliner, Martin A
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 04.04.1997
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
ENOLATE
DIASTEREOSELECTION
ROUTE
STEREOCHEMICAL CONTROL
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Summary:The ortho ester Claisen rearrangement of trisubstituted allylic alcohols exhibits significant levels of diastereoselection. In E allylic alcohols, a 1,3-diaxial interaction develops in the chairlike transition state leading to the anti isomer, rendering the reaction syn selective by a factor of 3−5 to 1. In Z allylic alcohols, the 1,3-diaxial interaction develops in the transition state leading to the syn isomer, generating an anti:syn selectivity of 6−15 to 1. The relative stereochemistry of the syn isomer was confirmed independently by the synthesis of the mycotoxin botryodiplodin.
Bibliography:ark:/67375/TPS-HQKFBR89-5
istex:2C3887F1A8769CCFE1F315607BA1A4F62319523F
Abstract published in Advance ACS Abstracts, March 1, 1997.
ObjectType-Article-1
SourceType-Scholarly Journals-1
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content type line 23
ISSN:0022-3263
1520-6904
DOI:10.1021/jo9614250