Stereoselective Synthesis of Glycomimetic Amines from Biomass Derived Cyrene

Cyrene, a low-cost commercial chiral compound widely available from the pyrolysis of cellulose containing materials including waste biomass, was employed in the preparation of secondary amines. The process exhibited nearly complete stereoselectivity for the D-manno configured amines (endo amines) within the 2,3,4-trideoxy hexose structure. Debenzylation of the N-benzylamine via catalytic hydrogenation provided the first synthesis of the diastereomerically pure primary amine, employable in turn for accessing the same (2S)-configured endo amines exclusively through reductive amination with aldehydes. This unprecedented access to pure endo amine furnishes a versatile chiral synthetic intermediate to nitrogenated glycomimetics.