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Design, Development, Mechanistic Elucidation, and Rational Optimization of a Tandem Ireland Claisen/Cope Rearrangement Reaction for Rapid Access to the (Iso)Cyclocitrinol Core

Author:
Plummer, Christopher W., Wei, Carolyn S., Yozwiak, Carrie E., Soheili, Arash, Smithback, Sara O., Leighton, James L.
Source:
Journal of the American Chemical Society 2014 v.136 no.28 pp. 9878-9881
ISSN:
1520-5126
Subject:
biosynthesis, chemical reactions, chemical structure, fungal proteins, temperature
Abstract:
An approach to the synthesis of the (iso)cyclocitrinol core structure is described. The key step is a tandem Ireland Claisen/Cope rearrangement sequence, wherein the Ireland Claisen rearrangement effects ring contraction to a strained 10-membered ring, and that strain in turn drives the Cope rearrangement under unusually mild thermal conditions. A major side product was identified as resulting from an unexpected and remarkably facile [1,3]-sigmatropic rearrangement, and a tactic to disfavor the [1,3] pathway and increase the efficiency of the tandem reaction was rationally devised.
Agid:
5391900