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3-Methyl-1-phenyl-2-phospholene and 1-phenyl-2-phospholene 1-oxides were converted into 2-bromo-3-hydroxy-3-methyl-1-phenylphospholane and 2-bromo-3-hydroxy-1-phenylphospholane 1-oxide (1-bromo-1,3,4-trideoxy-1,4-C-[(R, S)-phenylphosphinylidene]-glycero-tetrofuranose) by the action of bromine in aqueous medium. The bromo substituent of the phospholane was substituted by treatment with amines or an azide anion to afford novel glycoside derivatives of phosphanyl sugar analogs such as 2-amino-3-hydroxy-1-phenylphospholane (3,4-dideoxy-1,4-C-[(R, S)-phenylphosphinylidene]-glycero-tetrofuranosylamine) and 2-azido-3-hydroxy-3-methyl-1-phenylphospholane 1-oxides with retention of the configuration. The 1,3-dipolar cycloaddition of the 2-azido derivative of the phospholane with alkynes gave 3-hydroxy-3-methyl-1-phenyl-2-(triazol-1′-y1)phospholane 1-oxides as a novel triazole-derived nucleoside of phosphanyl sugar analogs. The structure of the glycoside and nucleoside derivatives of the phosphanyl sugar a...

Some phosphanyl sugar derivatives, which are analogs of sugars having a phosphorus atom in place of the ring oxygen, were synthesized from 2- and 3-phospholenes as starting materials. Catalytic cis-dihydroxylation of 2-phospholene or 3-phospholene 1-oxide derivatives with osmium(VIII) oxide in the presence of a cooxidant afforded 3-deoxy- or 1-deoxy-tetrofuranose-type phosphanyl sugar derivatives, respectively. cis- Dihydroxylation of 4-acyloxy-2-phospholene 1-oxide derivatives gave tetrofuranose type phosphanyl sugar derivatives. Some of these derivatives of phosphanyl sugars were subjected to structural analyses using 1H NMR and X-ray crystallography. 1. Presented at the XVIIIth Inlernational Carbohydrate Symposium, Milan, Italy, July 21-26, 1996.

Reaction of 2-bromo-3-hydroxy-1-methoxy-3-methylphospholane 1-oxide with silylated 2-hydroxypyridine gave a novel non-natural phosphono sugar nucleoside derivative.

Reaction of 2-bromo-3-hydroxy-1-methoxy-3-methylphospholane 1-oxide with silylated 2-hydroxypyridine gave a novel non-natural phosphono sugar nucleoside derivative.

Treatment of 1-phenyl-2-phospholene 1-oxide with N-bromoacetamide or bromine afforded threo and erythro bromohydrins, the latter being converted into novel N-glycosides by reaction with amines. The N-t-butyl phosphono sugar glycoside exists in the 2E conformation.

Treatment of 1-phenyl-2-phospholene 1-oxide with N-bromoacetamide or bromine afforded threo and erythro bromohydrins, the latter being converted into novel N-glycosides by reaction with amines. The N-t-butyl phosphono sugar glycoside exists in the 2E conformation.

Treatment of 1-phenyl-2-, and -3-phospholene 1-oxides with N-bromosuccinimide affords 4-bromo-1-phenyl-2-phospholene 1-oxide. Substitution of the bromide with acetate, followed by stereoselective oxidation with osmium tetroxide and peracetylation with acetic anhydride/pyridine affords phospho sugar derivatives of tetrafuranose. Furthermore, N-, O-, and S-glycosyl compounds of phospho sugars can be prepared from 3-methyl-1-phenyl-2-phospholene 1-oxide by bromination and nucleophilic substitution reactions. This is a novel and excellent route to prepare phospho sugar derivatives

Treatment of 1-phenyl-2-, and -3-phospholene 1-oxides with N-bromosuccinimide affords 4-bromo-1-phenyl-2-phospholene 1-oxide. Substitution of the bromide with acetate, followed by stereoselective oxidation with osmium tetroxide and peracetylation with acetic anhydride/pyridine affords phospho sugar derivatives of tetrafuranose. Furthermore, N-, O-, and S-glycosyl compounds of phospho sugars can be prepared from 3-methyl-1-phenyl-2-phospholene 1-oxide by bromination and nucleophilic substitution reactions. This is a novel and excellent route to prepare phospho sugar derivatives