The Condensation of D-Galactose with Nitromethane

Sowden, John C.; Strobach, Donald R.

doi:10.1021/ja01489a042

Cited by 59 publications

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“…Sowden (5,6) has shown that the sugar series may be ascended by reactions involving the condensation of nitromethane in -alkaline media with the aldehyde function of a glycose to give a mixture of epimeric 1-deoxy-1-nitroglycitols which on treatment with acid (Nef reaction (7)) yield the corresponding glycoses. This procedure, which avoids the use of hydrogen cyanide and the reduction of aMonolactones t o glycoses encountered in the use of the classical cyanohydrin method for the ascent of the sugar series (8), thus has several practical advantages.…”

Section: Discussionmentioning

confidence: 99%

THE SYNTHESIS OF D-glycero-D-manno-HEPTOSE

Hulyalkar¹,

Jones²,

Perry³

1963

Can. J. Chem.

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, whose mode of biosynthesis has been studied in this laboratory (3). In the course of these studies it became necessary to synthesize the heptose in order t o devise a method for its stepwise degradation to determine the 14C content a t the individual carbon atoms in its chain, and to prepare D-glycero-D-mannoheptose-1 -14C.D-glycero-D-manno-Heptose was first synthesised in 39% yield by the application of the Fisher cyanohydrin synthesis (4) to D-altrose. Sowden (5, 6) has shown that the sugar series may be ascended by reactions involving the condensation of nitromethane in -alkaline media with the aldehyde function of a glycose to give a mixture of epimeric 1-deoxy-1-nitroglycitols which on treatment with acid (Nef reaction (7)) yield the corresponding glycoses. This procedure, which avoids the use of hydrogen cyanide and the reduction of aMonolactones t o glycoses encountered in the use of the classical cyanohydrin method for the ascent of the sugar series (8), thus has several practical advantages.In the present work it was found that D-altrose could be condensed with nitromethane in alkaline methanol solution to give the theoretical yield of the nlixed crystalline salts of the epimeric 1-deoxy-1-nitroheptitols from which 1-deoxy-1-nitro-D-glycero-D-mannoheptitol was obtained crystalline in 46% bverall yield. Treatment of the soclium salt of the 1-deoxy-1-nitro-D-glycero-D-manno-heptitol with 6 N sulphuric acid gave a product containing mainly D-glycero-D-manno-heptose which was contaminated with some unchanged starting material, D-altrose, and some D-glycero-D-glz~co-heptose. Fractionation of this mixture by cellulose column chromatography (9) gave pure D-glycero-D-mannoheptose (60% yield), which remained a syrup. I t is considered that the procedure offers a convenient route for the synthesis of D-glycero-D-manno-heptose-1-14C using nitromethane-14C.Several derivatives of D-glycero-D-manno-heptose were prepared to investigate the possibility of using them for selective degradation studies directed to the determination of the distribution of 14C in the heptose found in the extracellular polysaccharide produced by Azotobacter indicum grown in the presence of 14C-labelled substrates. A degradation scheme for D-glycero-D-manno-heptose has been described in a recent paper (3).Attempts to prepare manno nose from the mixed anomeric methyl D-glycero-D-mannoheptopyranosides by selective scission of the exocyclic C8-c~ glycol system with periodate followed by reduction of the aldehyde group produced a t C6, in a way analogous to that used for the synthesis of D-gulose from D-glycero-D-gulo-heptose (lo), gave a low yield

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Section: Discussionmentioning

confidence: 99%

THE SYNTHESIS OF D-glycero-D-manno-HEPTOSE

Hulyalkar¹,

Jones²,

Perry³

1963

Can. J. Chem.

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“…20 Unless otherwise stated, the other materials were obtained from commercial suppliers and used without further purification. All the solvents and reagents, if it was necessary, were made anhydrous according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of new 2-substituted 3-amino-4-hydroxymethylthiophenes through intramolecular nitrile oxide cycloaddition processes and N,O-bond cleavage

Pistarà¹,

Corsaro²,

Chiacchio³

et al. 2011

Arkivoc

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A synthesis of new 2-substituted 3-amino-4-hydroxymethylthiophenes 7 is reported as a useful alternative to the long known oximation of oxothiophenes 8, followed by treatment with gaseous hydrochloric acid in a polar solvent. The synthesis consists of an INOC process of unsaturated sulfide nitrile oxides, obtained from the condensation of corresponding nitroalkenes and allylmercaptan and then dehydration, which leads to tetrahydrothieno [3,4-c]

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“…8 Hz, H-7), 3.92 (dd, 1H, J 10,11b ¼7.2 Hz, J 11a,11b ¼11.6 Hz, H-11b), 3.24 (s, 3H, OCH 3 ), 2.47 (ddd, 1H, H-6), 2.23 (br d, 1H, J 3a,3b ¼14. 8 Hz,, 2.05 (dd, 1H, H-3b), 2.13 (s, 3H, OAc), 2.12 (s, 3H, OAc), 2.07 (s, 3H, OAc), 2.03 (s, 3H, OAc), 1.43 (s, 3H, H-1a,1b,1c), 1.29 (s, 3H, CH 3 -5); 13 14), 281 (MÀ2HOAcÀC 2 H 2 OÀ2CH 3 ÀNO 2 , 13), 221 (MÀ3HOAcÀC 2 H 2 OÀ2CH 3 ÀNO 2 , 11), 207 (18), 149 (100), 147 (57), 133 (13), 105 (19), 95 (23), 91 (29); HRMS (FAB) calcd for C 22 H 33 NO 13 þNa 542.1849. Found 542.1853 (2R,3S)-1 0 -C-(1,4-dimethyl-3-exo-nitro-7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl)-D-galacto-pentitol (10) and 2,5-anhydro-1-deoxy-1-nitro-D-glycero-L-manno-or D-glycero-L-gluco-heptitol (11)…”

Section: Generalmentioning

confidence: 99%