D-Glucose-derived nitrones

Fisera, L, Al-Timara, U A R, Ertl, P, Pronayova, N, Preparation and stereoselectivity of 1,3-dipolar cycloaddition of D-glucose-derived nitrones to A-arylmaleimides, Monatsh. Chem., 124, 1019-1029, 1993. 

The synthesis began with conversion of D-glucose-derived compound 338 to aldehydofuranose 339. Reaction of 339 with benzylhydroxylamine in 2-fluoroethanol formed the corresponding nitrone 340 which spontaneously underwent 1,3-dipolar cycloaddition furnishing, after sequential NaI04 and NaBH4 treatment, the isoxazolidinocarbocycle 341. 

In 1982, Vasella and Voeffray [196] presented a synthesis of (+)-nojirimycin (5-amino-5-deoxy-D-glucose) using the 1,3-dipolar cycloaddition of a d-mannose-derived nitrone to furan. The chiral source in that synthesis (d-mannose) is not recovered. Jager and Muller used... 

The total synthesis of (+)-cyclophellitol containing a fully oxygenated cyclohexane ring was accomplished by T. Ishikawa and co-workers. The synthetic strategy was based on the intramolecular silyl nitronate [3+2] cycloaddition reaction. The cycloaddition precursor was prepared by the Henry reaction starting from a D-glucose-derived aldehyde. 

New polyhydroxylated quinolizidine and indolizidine derivatives (azasugars) were synthesised by intramolecular cycloaddition of a-D-glucose derived AI-(3-alkenyl)nitrones. The cycloadduct 87 was obtained as a unique diastereoisomer and transformed into 88 and 89 in two- and three-step sequence, respectively <01CC915>. 

Damodiran M, Sivakumar PM, SenthilKumar R, Muralid-haran D, Kumar BVNP, Doble M, Perumal PT. Antibacterial activity, quantitative structure-activity relationship and diastereoselective synthesis of isoxazolidine derivatives via 1,3-dipolar cycloaddition of )-glucose derived nitrone with olefin. Chem. Biol. Drug Des. 2009 74(5) 494-506. 

Intramolecular cycloadditions of chiral nitrones provide a useful tool for the preparation of bioactive heterocyclic compounds.63 Shing et al. demonstrated that 1,3-dipolar cycloaddition of nitrones derived from 3-0-allyl-hexoses is dependent only on the relative configuration at C-2,3, as shown in Scheme 8.16. Thus 3-0-allyl-D-glucose and -D-altrose (both with threo-configuration at C-2,3) produce oxepanes selectively, whereas 3-O-allyl-D-allose and -D-man-nose (both with erythro-configuration at C-2,3) give tetrahydropyranes selectively.80... 

The 1,3-dipolar cycloaddition of nitrone 12 (derived from D-glucose) was also used for the preparation of bicyclic aza sugars of type 14 (route a Fig. 5).12 Another classical approach (route b) allowed to prepare the analogs (e.g. 17).13,14... 

For the first time, DFT theory has been applied to a study of diastereofacial selectivity in 1,3-dipolar cycloadditions of nitrones to di-3,4-dimethylcyclobutene. ° The stereochemical outcome of the INAC reactions of nitrones (49) and (52) derived from 3-(9-allyl-D-hexoses is dependent only on the relative configuration at C(2,3), and thus 3-(9-allyl-D-glucose (48) and -o-altrose (threo configuration) afford oxepanes (50) selectively whereas 3-O-allyl-D-allose (51) and -D-mannose (erythro configuration) give tetrahydrofurans (53) and (54) selectively (Scheme 18). frani-2-Methylene-... 

The amino-oxazoline 37, and hence the trehalose inhibitor trehazolin 38, have been prepared by nitrone addition to a hexenal derivative obtained from D-glucose. Compound 38 has also been synthesized together with analogues 39 (both epimers) from myo-inositol to establish the correct structures of trehazolin and its epimer trehalostatin. >102... 

Application of the intramolecular nitrone-olefin cycloaddition to 3-0-allyl-o-glucose derivatives 49 and 50 and their D-allo isomers 51 and 52 furnished pyranoisoxazolidines 53 with varying degrees of diastereoselectivity. The main product obtained from 50 gave 54 on trimming of the side chain. ... 

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