Annie Duréault

Polyhydroxylated nortropanes starting from D-glucose : synthesis of homochiral (+) and (-)-calystegines B2

Abstract The cycloheptano-isoxazoline 1 , prepared from D-glucose, is converted to 6,7-dideoxy cycloheptitols which are suitable precursors for the synthesis of enantiomerically pure (+) and (−)-Calystegines B 2 .

Access to polyhydroxylated cycloheptane derivatives through stereoselective nitrile oxide intramolecular cycloaddition. Synthesis of an analogue of calystegine B2

Abstract A hydroxymethyl substituted calystegine B 2 has been synthesized stereoselectively by intramolecular cycloaddition of an olefinic nitrile oxide derived from D-glucose.

Synthesis and evaluation as glycosidase inhibitors of 2,5-imino-d-glucitol and 1,5-imino-d-mannitol related derivatives

Selectively functionalized 2,5-imino-D-glucitol and 1,5-imino-D-mannitol derivatives were synthesized and tested as precursors of hydrolytically resistant pseudo-disaccharides. Among them N-acetyl-6-amino-6-deoxy-2,5-imino-D-glucitol (11) and N-acetyl-6-amino-6-deoxy-1,5-imino-D-mannitol (12) were found potent and specific inhibitors against beta-D-glucosidase and alpha-L-fucosidase, respectively.

Diastereospecific synthesis of diaziridines from D-mannitol. Access to chiral α-aminoacids.

Abstract Nucleophilic opening of chiral diastereoisomeric diaziridines obtained from D- mannitol leads to precursors of D or L α-aminoacids (or aldehydes) and also provides a means of synthesizing polyhydroxylated piperidines.

Total enantiospecific syntheses of 13(S)-hydroxy 9Z, 11E-octadecadienoic (coriolic) acid and 13(S)-N-tosylamino analogue

Abstract The total syntheses of 13(S)-hydroxy 9Z, 11E-octadecadienoic (coriolic) acid and its 13(S)-N-tosylamino analogue are reported via a short, efficient, enantiospecific route from D-mannitol.

Synthesis of highly functionalized homochiral azetidines and azetidine-2-carboxylic esters

Abstract Homochiral (2S, 3S)-3-benzyloxy-2-formyl-azetidines 2, (2S, 3S)-3-benzyloxy-2-carbomethoxy-azetidines 3 and the highly strained (2S)-N-p-methoxyphenyl-2-silyloxymethyl-3-azetidinone 4 were successfully synthesized starting from diethyl-L-tartrate. The suitably functionalized azetidine ring is formed in a single synthetic operation with minimum protecting group chemistry.

2,5-disubstituted pyrrolidines from D-mannitol-derived bis-aziridines

Abstract Concise syntheses of 3,4-dihydroxy-2,5-disubstituted pyrrolidines have been achieved starting from D-mannitol-derived flexible L-Ido bis-aziridines. Nucleophilic ring opening of the N-Boc and the N-Cbz activated bis-aziridines by phenylthiolate and azide ions has been studied ; the reaction can be oriented either toward bis-opening (derivative A) or heterocyclization. Heterocyclization leads to a 1:9 mixture of the enantiopure polysubstituted piperidines B and pyrrolidines C.

One step synthesis of sulfur and nitrogen linked aza-disaccharide precursors from D-mannitol derived bis-aziridines

Abstract Carbon-nitrogen and carbon-sulfur linked pseudodisaccharides incorporating an hydroxylated pyrrolidine type glucosidase inhibitor have been prepared. These new azasugar-containing disaccharides result from the nucleophilic opening of D-mannitol derived bis-aziridines either by 3-deoxy-3-amino-D-glucose or by 3-deoxy-3-thio-D-glucose.

Practical route to D-manno and D-gluco azasugars from C2 symmetric bis-aziridines

6-Amino-2,5-imino-D-glucitol 2 and 6-amino-1,5-imino-D-mannitol 3, substituted by a free hydroxyl group, have been synthesized from the conformationally flexible N-Boc bis-aziridine 1. Regioselective ring-opening of 1 by acetic acid is a straight way towards 2, while reaction of 1 with water or allylic alcohol under ytterbium triflate catalysis produces selectively the azapyranose 3. Nitrous deamination carried out on the cyclic carbamate-protected pyrrolidine 4 leads to a 1:1 mixture of both 2,5-imino-D-glucitols 5 and 6 bearing a free hydroxyl substituent either at C-1 or at C-6.

An enantiospecific synthesis of polyoxamic acid from L-arabinose

Abstract Polyoxamic acid, 2-amino-2-deoxy-L-xylonic acid, is synthetized by thiophenoxide opening of a five-carbon chiral hydroxylated aziridine easily derived from L-arabinose. The formation of the carboxy group resulted from a Pummerer reaction.