Characterization and interconversions of 2-S-ethyl-2-thio-D-mannose diethyl dithioacetal and the facile epimerization of 2-thio-D-mannopyranose derivatives.
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-alpha-D-mannofuranoside (5). Complete demercaptalation of 4 affords syrup 2-S-ethyl-2-thio-D-mannopyranose (6), which was characterized as its phenylhydrazone 7 and the crystalline alpha-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-beta-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-alpha-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.
Horton
D
D
Department of Chemistry, American University, Washington, DC 20016, USA.
Norris
P
P
Berrang
B
B
D000080:Acetals / Q000138:chemical synthesis / Q000737:chemistry; D002236:Carbohydrate Conformation; D005947:Glucose / Q000031:analogs & derivatives; D009682:Magnetic Resonance Spectroscopy; D008358:Mannose / Q000031:analogs & derivatives*; D008968:Molecular Conformation; D015394:Molecular Structure; D013440:Sulfides / Q000138:chemical synthesis / Q000737:chemistry*
D000080:Acetals; D013440:Sulfides; D005947:Glucose; D008358:Mannose