Serendipitous one-pot synthesis of chiral dienes from pyranosidic 2,4-bistriflates

Abstract

Attempted nucleophilic displacements of l-rhamnosyl 2,4-bistriflates led to serendipitous formation of a chiral diene via competing cascade eliminations. The reaction also followed the same pathway with d-rhamnosyl and d-mannosyl 2,4-bistriflates substrates providing access to dienes with opposite stereochemistry. The reaction presumably proceeds through E2 elimination of C2 triflate followed by allylic rearrangement. The easily accessible chiral dienes would be useful in the synthesis of natural products.

Keywords: 2,4-bistriflates; Chiral diene; S(N)2 versus E2; d-mannose; l-rhamnose.