Synthesis of intermediates in the formation of hydroxy piperidines and 2-azido lactones from d-erythrose

A new stereodivergent synthesis towards piperidine iminosugar and azido lactones is described. The reaction of ethylidene-d-erythrose with amide sulfur ylides gave two isomeric trans-epoxyamides which were converted to 2-azido derivatives. Hydrolysis of the allo isomer gave 2-azido-1,4-lactone while the manno isomer gave the open chain epoxyamide. The latter gave a DMJ derivative in two steps. Direct hydrolysis of ethylidene epoxyamides gave the 3,6-anhydro glyconamides.

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2-Azido-2-deoxy-3,5-di-O-benzyl-d-allono-1,4-lactoneC20H21N3O5[α]D27=+11 (c 1.8, CH2Cl2).Source of chirality: d-erythrose and stereoselective synthesis

1,5-Dideoxy-1,5-imino-2,4-di-O-benzyl-N,N-diethyl-d-mannopyranosiduronamideC24H32N2O4[α]D27=-83 (c 1.1, CH2Cl2)Source of chirality: d-erythrose, stereoselective synthesis and stereospecific cyclization

2,4-Di-O-Benzyl-1-deoxymannojirimicinC20H25NO4[α]D27=-5.5 (c 0.7, CH2Cl2)Source of chirality: d-erythrose, stereoselective synthesis and stereospecific cyclization

2-Azido-N,N-dibenzyl-4,6-O-ethylidene-d-allo-hexonamideC22H26N4O5[α]D25=-171 (c 1, CH2Cl2)Source of chirality: d-erythrose and stereoselective synthesis

2-Azido-N,N-dibenzyl-4,6-O-ethylidene-d-manno-hexonamideC22H26N4O5[α]D25=+40 (c 0.8, CH2Cl2)Source of chirality: d-erythrose and stereoselective synthesis

2-Azido-2-deoxy-d-allono-1,4-lactoneC6H9N3O5[α]D20=-3.5 (c 1.3, MeOH)Source of chirality: d-erythrose and stereoselective synthesis