SYNTHETIC STUDIES ON QUEBRACHITOL .2. SYNTHESIS OF SEVERAL OPTICALLY-ACTIVE O-METHYL-INOSAMINES AND O-METHYL-INOSADIAMINES FROM L-QUEBRACHITOL

A series of p-toluenesulfonic and methanesulfonic esters of L-quebrachitol have been prepared starting from the di-O-isopropylidene derivative of the cyclitol. Nucleophilic displacement of these sulfonates with azide ion in 2-methoxyethanol produced the azido compounds, hydrogenolysis of which with Raney nickel, followed by acetylation, gave thirteen optically active O-methyl-inosamine and two O-methyl-inosadiamine derivatives. The structures of the new aminocyclitols were established on the basis of H-1-n.m.r. spectral data for the corresponding per-O-acetyl derivatives. The mechanisms of the substitution reactions, involving mainly neighboring-group participation, are discussed.