Non-canonical regioisomerizations and a 'Diels-Alderase' are likely essential in the biosynthesis of spiculoic acid A.
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.
Department of Chemistry, Syracuse University, Syracuse, NY 13244, USA.
Atahualpa
A
Pinto
Christopher N
CN
Boddy
D055162:Biocatalysis; D002264:Carboxylic Acids / Q000737:chemistry / Q000378:metabolism*; D003500:Cyclization; D007189:Indans / Q000737:chemistry / Q000378:metabolism*; D048630:Polyketide Synthases / Q000378:metabolism*; D013237:Stereoisomerism
D002264:Carboxylic Acids; D007189:Indans; C490145:spiculoic acid A; D048630:Polyketide Synthases