The Role of Total Synthesis in Structure Revision and Elucidation of Decanolides (Nonanolides)

Ten-membered lactones are commonly observed structures of natural products. They are mostly fungal metabolites, which often act as plant pathogens, but recently ten-membered lactones were identified as pheromones of frogs and termites. Although modern spectroscopic methods are nowadays routinely used to elucidate the structure of natural products, structural assignments of ten-membered lactones often remain incomplete or are surprisingly often erroneous. Most errors concern the absolute configuration. The examples discussed in this chapter demonstrate that enantioselective total synthesis is not only an efficient tool for corroborating or revising a proposed structure, but that the synthesis of different stereoisomers as references for gas chromatographic investigations can be a vital part of the structure elucidation process if only minute amounts of material are available. As a method of outstanding importance for the synthesis of ten-membered lactones olefin metathesis has emerged. Most of the examples discussed herein use one or more olefin metathesis reactions as key steps.