Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan/Azodicarbonsäurediethylester, 4. Mitt.: Transformationen an Mannose und Galaktose

Reaction of methyl -D-galactopyranoside (1) with two equivalents oft-butyldimethylchlorosilane yields methyl 2,6-bis-O-(tBDMSi)--D-galactopyranoside (1 b), methyl 3,6-bis-O-(tBDMSi)--D-galactopyranoside (1 c) and methyl 4,6-bis-O-(tBDMSi)--D-galactopyranoside (1 d). Likewise methyl -D-mannopyranoside (6) affords methyl 2,6-bis-O-(tBDMSi)--D-mannopyranoside (6 d) and methyl 3,6-bis-O-(tBDMSi)--D-mannopyranoside (6 b), which can be isomerised withTPP/DEAD to methyl 4,6-bis-O-(tBDMSi)--D-mannopyranoside (6 f). Methyl 6-O-(tBDMSi)--D-galactopyranoside (1 a) and methyl 6-O-(tBDMSi)--D-mannopyranoside (6 a) can be prepared from1 or6 with one equivalent oft-butyldimethylchlorosilane.Without an external nucleophile the sugar derivatives1 a and1 b react withTPP/DEAD to form the 3,4-carbonato--D-galactopyranosides1 h and1 i and the 3,4-carbonato-2-O-ethoxycarbonyl--D-galactoside (1 j). In contrast to the formation of the compound1 i by means ofTPP/DEAD the reaction of1 a withTPP and Di-t-butyl-azodicarboxylate (DTBAD) yields the 2,3-anhydro--D-taloside (4 b) and only a small amount of1 i. The epoxide4 b can be cleaved withp-nitrobenzoylchloride/pyridine to the 3-chloro-3-deoxy-2,6-di-O-p-nitrobenzoyl--D-idoside (5). Reaction of1 c and1 d withTPP/DEAD yields the 2,3-anhydro--D-gulopyranoside (2), which can be transformed with NaN₃/NH₄Cl to the 2-azido-2-deoxy--D-idopyranoside (3).Likewise6 a and6 d can be converted to the 3,4-anhydro--D-talosides (7 a and7 b). Reaction of7 b or6 d withTPP/DEAD/NH₃ leads to 3,4-anhydro-2-azido-2-deoxy--D-galactopyranoside (8) and 3-azido-3-deoxy--D-altropyranoside (10), resp.The epoxide7 b is opened with NaN₃/NH₄Cl to the 4-azido-4-deoxymannosides (11 a and11 c) and the 3-azido-3-deoxy--D-idopyranoside (12), while the epoxide8 affords the 2,4-di-azido-2,4-dideoxy--D-glucopyranoside (9).Structures were elucidated by¹H-NMR-analysis of the corresponding acetates.

H. H. Brandstetter undE. Zbiral, Helv., im Druck.