De novo asymmetric synthesis and biological analysis of the daumone pheromones in Caenorhabditis elegans and in the soybean cyst nematode Heterodera glycines

摘要

The de novo asymmetric total syntheses of daumone 1, daumone 3 along with 5 new analogs are described. The key steps of our approach are: the diastereoselective palladium catalyzed glycosylation reaction; the Noyori reduction of 2-acetylfuran and an ynone, which introduce the absolute stereo chemistry of the sugar and aglycon portion of daumone; and an Achmatowicz rearrangement, an epoxidation and a ring opening installing the remaining asymmetry of daumone. The synthetic daumones 1 and 3 as well as related analogs were evaluated for dauer activity in Caenorhabditis elegans and for effects on hatching of the related nematode Heterodera glycines. This data provides additional structure activity relationships (SAR) that further inform the study of nematode signaling. (C) 2016 Elsevier Ltd. All rights reserved.