Synthesis and Comparative Antibacterial Activity of Verdamicin C2 and C2a. A New Oxidation of Primary Allylic Azides in Dihydro[2<i>H</i>]pyrans

Abstract

A synthesis of verdamicin C2 and its congener C2a has been accomplished from sisomicin relying on a novel oxidative transformation of an allylic azide to the corresponding alpha,beta-unsaturated aldehyde, and its stereocontrolled elaboration into the intended 5' side chain of verdamicin C2 and C2a. In vitro antibacterial testing shows that both C6' epimers in verdamicin C2 and C2a are equally active against a variety of bacterial strains. Oxidation of allylic primary azides, ethers, and esters of 2-substituted dihydro[2H]pyrans with SeO(2) leads directly to the corresponding aldehydes.