The Total Synthesis of (±)-lsonitrin B (Deoxytrichoviridin)

The total synthesis of (±)-isonitrin B (5; deoxytrichoviridin) is presented. The carbon framework is readily constructed using a [4 + 2] cycloaddition between 1-acetylcyclopentadiene (11) and the acyl-nitroso dienophile 16. Novel methods for the preparation of vinyl formamides from thiooximes under very mild conditions and their subsequent dehydration to give vinyl isonitriles are outlined in the synthesis. The first ever synthesis of unsubstituted epoxy isonitriles is also described. 1. Introduction 2. Synthesis of the Carbon Skeleton 3. Preparation of Vinyl Formamides and Vinyl Isonitriles. New Synthetic Methods 4. The Synthesis of Epoxy Isonitriles