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C-glycoside syntheses: Part I. Dendritic syntheses of hexose and aminohexose C-pyranosides from 2,6-anhydro-5,7-O-benzylidene-1-deoxy-1-nitro-D-guloheptitol (82). Part II. Henry condensation of nitroethane and nitropropane with 4,6-O-benzylidene-D-glucopyranose (81)

Date of Award


Document Type

Dissertation - Pacific Access Restricted

Degree Name

Doctor of Philosophy (Ph.D.)



First Advisor

Paul Gross


Part I. The di-O-acetyl derivative of 4,6-O-benzylidene-1-deoxy-1-nitromethyl-$\beta$-D-glucopyranose was reduced by a mixture of elemental iron and nickel in aqueous tetrahydrofuran under CO$\sb2$, with concurrent O $\to$ N acetyl migration to 1-acetamido-4-O-acetyl-2,6-anhydro-5,7-O-benzylidene-$ 1$-deoxy-D-glycero-D-guloheptitol. Its 2-O-mesyl derivative was converted by base into the D-manno-2,3-epoxide. The epoxide ring was opened by NH$\sb3$ to give the 3-amino-$\beta$-D-altropyranose derivative, which was subsequently N-benzoylated to 1-acetamido-2,6-anhydro-4-benzoylamido-5,7-O-benzylidene-1,$4 $-dideoxy-D-glycero-D-glucoheptitol. Attempts to prepare 1-acetamido-2,6-anhydro-4-benzoylamido-5,7-O-benzylidene-1,$ 4$-dideoxy-3-methanesulfonyl-D-glycero-D-glucoheptitol gave spontaneously the D-allo-oxazoline derivative. However, a 3-O-mesyl derivative could be obtained by mesylation of 1,4-di-acetamido-2,6-anhydro-5,7-O-benzylidene-1,$4 $-dideoxy-D-glycero-D-glucoheptitol. 2,6-Anhydro-5,7-O-benzylidene-1-deoxy-$1 $-nitro-D-glycero-D-guloheptitol was reduced and N-acetylated to the acetamidomethyl derivative. 3,4-Di-O-mesylation of 1-acetamido-2,6-anhydro-5,7-O-benzylidene-$1 $-deoxy-D-glycero-D-guloheptitol gave 1-acetamido-2,6-anhydro-5,7-O-benzylidene-1-deoxy-3,$4 $-dimethanesulfonyl-D-glycero-D-guloheptitol, which reacted with methoxide to give the D-manno-2,3-epoxide, and mostly 2,6-anhydro-5,7-O-benzylidene-1-deoxy-D-glycero-D-glucoheptitol $\lbrack1,2,3, : 4\sp\prime,5\sp\prime,6\sp\prime$) -2$\sp\prime$-methyl-2$\sp\prime$-oxazine, presumably via a D-allo-2,3-epoxide. Part II. The condensation of 4,6-O-benzylidene-D-glucopyranose with nitroethane gave 2,6-anhydro-1,3-O-benzylidene-7,8-dideoxy-$7 $-nitro-D-threo-L-gulooctitol and its diastereomer, which was obtained by an acetylation-deacetylation procedure 2,6-Anhydro-1,3-O-benzylidene-7,8-dideoxy-$7 $-nitro-L-erythro-L-gulooctitol was reduced by a mixture of elemental Fe$\sp\circ$/Ni$\sp\circ$ in aqueous THF under CO$\sb2$ to 7-amino-2,6-anhydro-1,3-O-benzylidene-7,$8 $-dideoxy-L-erythro-L-gulooctitol with retention of the 4,6-O-benzylidene blocking group. Acetylation of 2,6-anhydro-1,3-O-benzylidene-7,8-dideoxy-7-nitro-D-threo-L-gulooctitol produced an open chain compound. Cyclic product was not isolated. The oxime derivative, 4,5-di-O-acetyl-3,7-anhydro-6,8-O-benzylidene 1,2-dideoxy-2-oxime-D-glycero-D-guloheptitol, was separated as a byproduct from the acetylation. The condensation of nitropropane with 4,6-O-benzylidene-$\beta$-D-glucopyranose, followed by acetylation of the reaction solution, gave 4,5-di-O-acetyl-2,6-anhydro-1,3-O-benzylidene-7-nitro-7,8,$9 $-trideoxy-D-threo-L-gulononitol and its diastereomer. Deacetylation of 4,5-di-O-acetyl-2,6-anhydro-1,3-O-benzylidene-7-nitro-7,8,$9 $-trideoxy-D-threo-L-gulononitol gave 2,6-anhydro-1,3-O-benzylidene-7-nitro-7,8,$9 $-trideoxy-D-threo-L-gulononitol, which could be reduced to the free amino compound by a mixture of elemental Fe$\sp\circ$/Ni$\sp\circ$ in aqueous THF under CO$\sb2$.



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