Facile syntheses of pseudo-α-D-glucopyranose and pseudo-α-D-mannopyranose

Abstract

Pseudo-a-D-glucopyranose 1 and pseudo-a-D-mannopyranose 2 are obtained via a stereoselective cisand trans-hydroxylation respectively of the alkene 8, which is readily derived from (-)-quinic acid.

Carbohydrates to carbocycles: an expedient synthesis of pseudo-sugars

“…Vandewalle 10 prepared eight pseudo-sugars belonging to the allo, gulo, manno and talo series which possess 2,3-cis-diol units from (1R,2S,3R,4S)-4-butyryloxy-2,3-(propane-2,2-diyldioxy)cyclohex-5-en-1-ol. The synthetic versatility of quinic acid was demonstrated by Shing in his synthesis of pseudo-b-d-manno-, 11 pseudo-b-d-fructo-, 11 pseudo-a-dgluco- 12 and pseudo-a-d-manno-pyranoses. 12 Ferrier prepared crystalline pseudo-a-d-glucopyranose 13 from 2-deoxyinosose.…”

“…The synthetic versatility of quinic acid was demonstrated by Shing in his synthesis of pseudo-b-d-manno-, 11 pseudo-b-d-fructo-, 11 pseudo-a-dgluco- 12 and pseudo-a-d-manno-pyranoses. 12 Ferrier prepared crystalline pseudo-a-d-glucopyranose 13 from 2-deoxyinosose.…”

“…17 Purification and separation by preparative TLC of the partially benzylated mixture gave 10 and 11 in 34 and 26% yields, respectively. Deprotection under similar conditions as those for ii 100% ii 100% 66% v HO HO 7 gave pseudo-a-mannopyranose 12, [a] D +1.5 (c 0.4, MeOH) [lit., 12 [a] D +1.9 (c 1.0, MeOH)], and pseudo-b-d-glucopyranose 13, [a] D +10.0 (c 0.3, H 2 O) [lit., 18 [a] D +10.9 (c 0.83, H 2 O)], from 10 and 11, respectively, in quantitative yields (Scheme 3).…”

Hydroxyalkylation of 6‐aminouracil

“…3 6-AU gives barbituric acid when heated with concentrated hydrochloric acid or with sulfuric(VI) acid. 3,4 6-AU and its alkyl-, aryl-, and hydroxyalkyl-derivatives are semiproducts in the synthesis of drugs used for heart diseases, 5-8 asthma, 9,10 tumor, [11][12][13] allergy, 14,15 and depression. 16 Hydroxyalkyl derivatives of 6-AU can be prepared in the reaction of cyanoacetic acid with N-(2hydroxyethyl)urea (1-or 3-substituted derivatives) 6 and in the reaction of 6-chlorouracil, or 6-AU, or their 1,3dialkyl derivatives with aminoalcohols, e.g., 2-aminoethanol or 3-aminopropanol (substituted derivatives at N atom of amine group).…”

An Orthogonally Protected Cyclitol for the Construction of Nigerose- and Dextran-Mimetic Cyclophellitols

“…mushroom and is a potent irreversible inhibitor of retaining β-exoglucosidases. 1 , 2 Since its discovery, a number of syntheses of cyclophellitol have appeared in the literature. 3 − 6 Cyclophellitol is a densely functionalized cyclohexane featuring the β- d -glucopyranose configuration with an epoxide bridging C1 and C7.…”