Reactions of relevance to the chemistry of aminoglycoside antibiotics. Part 14. A useful radical-deamination reaction

Abstract

Primary, secondary, and tertiary aliphatic or alicyclic isocyanides are smoothly reduced under radical conditions using tri-n-butylstannane to the corresponding hydrocarbons. The relative ease of reduction is tertiary > secondary > primary. Aromatic isocyanides are not reduced under these conditions. The reduction of isothiocyanates (or isoselenocyanates) by tri-n-butylstannane also affords hydrocarbons, but here the isocyanides have been shown to be intermediates. The reduction of a compound with isocyanide and xanthate functions in a 1,2-relationship gives a smooth radical fragmentation to furnish an olefin. An efficient synthesis of 2-deoxy-D-glucose starting with glucosamine is described.