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Facile Orthoester Formation in a Model Compound of the Taxol Oxetane: Are Biologically Active Epoxy Esters, Orthoesters, and Oxetanyl Esters Latent Electrophiles?
Author(s) -
Giner JoséLuis,
Faraldos Juan A.
Publication year - 2003
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200390306
Subject(s) - orthoester , chemistry , oxetane , electrophile , hydrolysis , organic chemistry , catalysis
A steroidal oxetanyl ester was synthesized in eight steps as a biomimetic model of taxol oxetane. The model compound was surprisingly reactive under acidic conditions, rearranging in the absence of H 2 O to a [2.2.1]‐bicyclic orthoester. Both the oxetanyl ester and the orthoester readily hydrolyze to produce the same triol monoacetate. On the basis of the oxetanyl ester/orthoester rearrangement, a novel biochemical function is suggested for the epoxy esters and oxetanyl esters found in taxoids whereby dioxonium ions, generated from these functional groups, react with cellular proteins to form mixed orthoesters or ethers. A similar process could be involved in the mechanism of action of natural orthoesters such as resiniferatoxin.