Non-canonical regioisomerizations and a 'Diels-Alderase' are likely essential in the biosynthesis of spiculoic acid A.

Abstract

The regiochemistry of dehydration and cyclization steps of the linear biosynthetic precursor of the polyketide natural product Spiculoic acid A (1) were examined. Herein we describe the synthesis of polyene-containing aldehyde 21, a counterpart to the metabolite's putative polyketide intermediate and demonstrate its inability to undergo facile IMDA chemistry. These results suggest the involvement of a non-canonical regioisomerization in the biosynthesis of 1, and that the IMDA reaction is likely enzyme-catalyzed.

• Authors: Atahualpa Pinto, Christopher N Boddy
• Journal: Bioorganic & medicinal chemistry letters (Bioorg Med Chem Lett) Vol. 22 Issue 16 Pg. 5253-6 (Aug 15 2012) ISSN: 1464-3405 [Electronic] England
• PMID: 22801647 (Publication Type: Journal Article, Research Support, Non-U.S. Gov't, Research Support, U.S. Gov't, Non-P.H.S.)
• Copyright: Copyright © 2012 Elsevier Ltd. All rights reserved.

Chemical References

• Carboxylic Acids
• Indans
• spiculoic acid A
• Polyketide Synthases

Topics

• Biocatalysis
• Carboxylic Acids (chemistry, metabolism)
• Cyclization
• Indans (chemistry, metabolism)
• Polyketide Synthases (metabolism)
• Stereoisomerism