Synthesis of Rare‐Bacterial Sugar Analogs: Thomosamine and Fluorinated Thomosamine

Bacterial carbohydrates that include unusual deoxy amino sugars represent interesting targets in drug discovery. The chemical synthesis of such probes and fluorinated analogs is a challenge that needs to be addressed. In this work, a novel approach to thomosamine (4‐amino‐4,6‐dideoxy‐ d ‐galactopyranose ( d ‐Fuc p 4N)) and fluorinated thomosamines from levoglucosan (1,6‐anhydro‐ β ‐ d ‐glucopyranose) is developed. The key steps involve the introduction of the C4 amino on 1,6‐anhydro bridged intermediates and the subsequent C6 reduction. Thomosamine, 3‐deoxy‐3‐fluoro‐thomosamine, and 2,3‐dideoxy‐2,3‐difluoro‐thomosamine are accessed as their protected form with a thiophenyl group at the anomeric position.