Radical Decarboxylative Cyanomethylation of Aliphatic Carboxylic Acids and Uronic Acids via Vinyl Azide Cascade Fragmentation

A direct oxidative radical decarboxylative cyanomethylation of carboxylic acids is described using 3-azido-2-methylbut-3-en-2-ol as the carbon-centered radical acceptor. The transformation is applicable to structurally diverse a-amino acids, a-oxy acids, a-keto acids, pentofuranuronic acids, and hexopyranuronic acids. The mechanistic investigations suggest that a radical process is involved in the transformation. This work provides a potential approach to beta-amino acid, 5-deoxy-hexofuranose, and 6-deoxy-heptose constructs of biological relevance.