Characterization and interconversions of 2-S-ethyl-2-thio-d-mannose diethyl dithioacetal and the facile epimerization of 2-thio-d-mannopyranose derivatives

Add time:07/18/2019    Source:sciencedirect.com

3,4,5,6-Tetra-O-benzoyl-d-glucose diethyl dithioacetal (2) reacts with ethanethiol under acidic conditions to afford 3,4,5,6-tetra-O-benzoyl-2-S-ethyl-2-thio-d-mannose (3), the stereochemistry at C-2 of which has been assigned by chemical conversions on its debenzoylated derivative, the crystalline 2-S-ethyl-2-thio-d-mannose diethyl dithioacetal (4). In the presence of mercuric chloride (1.1 molar equiv), 4 is converted into crystalline ethyl 2-S-ethyl-1,2-dithio-α-d-mannofuranoside (5). Complete demercaptalation of 4 affords syrupy 2-S-ethyl-2-thio-d-mannopyranose (6), which was characterized as its phenylhydrazone 7 and the crystalline α-pyranose tetraacetate 9. Extended treatment of 4 with mercuric chloride and aqueous sodium hydrogencarbonate resulted in isolation of 6, along with its crystalline 2-epimer, 2-S-ethyl-2-thio-β-d-glucopyranose (10). Remercaptalation of 6 affords the manno diethyl dithioacetal 4 as the major product, whereas similar treatment of 10 yields ethyl 2-S-ethyl-1,2-dithio-α-d-glucopyranoside (13). The mechanism of conversion of 2 into 3, as well as the unusually facile interconversion of 2-S-ethyl-2-thio-d-mannose (6) and its d-gluco epimer 10, has been investigated.

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