The Role of Acyloxyphosphonium Ions and the Stereochemical Influence of Base in the Phosphorane-Mediated Esterification of Alcohols

Intimate details of the Mitsunobu mechanism: The trapping of an acyloxytributylphosphonium ion with a chiral secondary alcohol leads to either retention or inversion of stereochemistry in the resulting ester depending on the exclusion or inclusion of a base (see scheme). Insight into the mechanism o...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2003-09, Vol.42 (34), p.4051-4054
Main Authors: McNulty, James, Capretta, Alfredo, Laritchev, Vladimir, Dyck, Jeff, Robertson, Al J.
Format: Article
Language:English
Subjects:
acylation
amines
peroxides
phosphanes
synthetic methods
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Summary:Intimate details of the Mitsunobu mechanism: The trapping of an acyloxytributylphosphonium ion with a chiral secondary alcohol leads to either retention or inversion of stereochemistry in the resulting ester depending on the exclusion or inclusion of a base (see scheme). Insight into the mechanism of phosphorane‐mediated esterification processes is presented.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200351209