* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With hydrogenchloride In water; acetone at 18 - 20℃; for 0.0833333 h;
To a solution of the orthoester4(4.4 g, 12 mmol) in anhydrous acetone (27 mL) was added 1M hydrochloric acid (HCl) aq. (2.7 mL) in one portion with vigorous stirring (~18°C, water bath). After being stirred for an additional 5 min at room temperature, the reaction mixture was concentrated on a rotary evaporator below 20°C. The resulting solid was dissolved in CHCl3(25 mL) and washed with water (2 × 10 mL). The organic layer was dried over anhydrous Na2SO4, filtered, and concentrated on a rotary evaporator. The residue was triturated with diethyl ether (Et2O) and recrystallized from EtOH to yield the tetraacetyl mannose5(1.9 g, 45percent) as a white solid.Rfvalue 0.13 (hexane : EtOAc = 1 : 1). m.p. 134–136°C. HRMS (ESI):m/zfor C14H20NaO10([M+Na]+) cacld 371.09542, found 71.09581 (error 0.39 mmu, 1.06 ppm).
26%
With hydrogenchloride In water; acetone at 20℃; for 0.166667 h;
To a solution of compound 10 (11.24 g, 30 mmol) in acetone (40 ml),1M HCl (aq) was added in one portion while vigorously stirring in a water bath. The mixture was stirred at room temperature for 10 min. It was then concentrated under reduced pressure. CHCl3 was added. The resulting mixture was washed with water. After separation, the organic layer was dried over Na2SO4, concentrated, and washed with ether and EtOH to give 2.73 g of 11 as a white solid. Yield: 26percent.
Reference:
[1] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1848 - 1858
[2] Tetrahedron, 1992, vol. 48, # 47, p. 10249 - 10264
[3] Tetrahedron Letters, 2013, vol. 54, # 17, p. 2190 - 2193
Reference:
[1] Chemische Berichte, 1930, vol. 63, p. 386,390
[2] Journal of the American Chemical Society, 1958, vol. 80, p. 3372,3378[3] Journal of the American Chemical Society, 1959, vol. 81, p. 5171,5172, 5176
[4] Tetrahedron Letters, 2013, vol. 54, # 17, p. 2190 - 2193
[5] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1848 - 1858
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1995, # 22, p. 2883 - 2898
[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1995, # 22, p. 2883 - 2898
7
[ 83-87-4 ]
[ 18968-05-3 ]
Reference:
[1] Tetrahedron, 1992, vol. 48, # 47, p. 10249 - 10264
[2] Tetrahedron Letters, 2013, vol. 54, # 17, p. 2190 - 2193
[3] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1848 - 1858
Reference:
[1] Zhurnal Obshchei Khimii, 1952, vol. 22, p. 247,249; engl. Ausg. S. 303, 304
15
[ 6087-47-4 ]
[ 18968-05-3 ]
Reference:
[1] Zhurnal Obshchei Khimii, 1952, vol. 22, p. 247,249; engl. Ausg. S. 303, 304
16
[ 3458-28-4 ]
[ 108-24-7 ]
[ 18968-05-3 ]
Reference:
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1981, vol. 30, # 7, p. 1329 - 1331[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1981, # 7, p. 1638 - 1641
17
[ 358-23-6 ]
[ 18968-05-3 ]
[ 92051-23-5 ]
Yield
Reaction Conditions
Operation in experiment
56%
With pyridine In dichloromethane at -15 - 20℃; Inert atmosphere
The tetraacetyl mannose5(1.8 g, 5 mmol) was dissolved in anhydrous CH2Cl2(14 mL) containing dry pyridine (0.9 mL, 11 mmol). This solution was cooled to -15°C and trifluoromethanesulfonic anhydride (triflic anhydride) (0.9 mL, 5.2 mmol) was added dropwise over a period of 25 min under a nitrogen atmosphere with vigorous stirring. The mixture was then allowed to reach room temperature overnight. The reaction mixture was successively washed with ice-cold saturated aqueous NaHCO3(50 mL) and water (50 mL). The organic layer was dried over anhydrous Na2SO4, filtered, and concentrated on a rotary evaporator.2-Tf-O-AcManwas isolated by column chromatography on silica with hexane :EtOAc=1: 1 as the eluant as white solid(1.4 g, 56percent).Rfvalue 0.5 (hexane : EtOAc = 1 : 1).
Reference:
[1] Tetrahedron, 1992, vol. 48, # 47, p. 10249 - 10264
[2] Journal of the American Chemical Society, 2010, vol. 132, # 21, p. 7405 - 7417
[3] Carbohydrate Research, 1991, vol. 210, p. 333 - 337
[4] Organic and Biomolecular Chemistry, 2009, vol. 7, # 3, p. 564 - 575
[5] Carbohydrate Research, 1984, vol. 128, p. 291 - 296
[6] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1848 - 1858
[7] Carbohydrate Research, 1993, vol. 245, # 2, p. 219 - 231
[8] Tetrahedron Asymmetry, 2005, vol. 16, # 2, p. 321 - 335
[9] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 2, p. 444 - 447
[10] Acta Crystallographica Section C: Crystal Structure Communications, 2012, vol. 68, # 9, p. o338-o340
18
[ 18968-05-3 ]
[ 92051-23-5 ]
Yield
Reaction Conditions
Operation in experiment
77%
With pyridine; trifluoromethanesulfonic acid anhydride In dichloromethane
To a solution of mannose tetraacetate 55 (1.50 g. 4.30 mmol) in 46 mL of CH2 Cl2 is added pyridine (1.0 mL, 13 mmol). The solution is cooled to -25° C. and trifluoromethanesulfonic anhydride (1.8 mL, 2.98 g, 10.5 mmol) is added dropwise. The reaction mixture is stirred for 45 min at -25° C. and then diluted with 50 mL of CH2 Cl2, washed with H2 O (100 mL), NaHCO3 (100 mL), saturated NaCl (100 mL), dried over MgSO4, filtered, and concentrated to afford an orange gel. The product is recrystallized from diethyl ether (25 mL) to afford 1.59 g (77percent) of 1,3,4,6-tetra-O-acetyl-2-O-trifluoromethanesulfonyl-β-D-mannopyranose 56 as a white solid: Rf 0.49 (50percent EtOAc/hexane); 1 H NMR (CDCl3, 300 MHz) δ 5.92 (s, 1H, H-1), 5.15-5.34 (m, 3H), 4.154.28 (m, 2H), 3.81-3.87 (m, 1H, H-5), 2.08 (s, 3H), 2.10 (s, 3H), 2.12 (s, 3H), 2.16 (s,3H).
With pyridine; In dichloromethane; at -15 - 20℃;Inert atmosphere;
The tetraacetyl mannose5(1.8 g, 5 mmol) was dissolved in anhydrous CH2Cl2(14 mL) containing dry pyridine (0.9 mL, 11 mmol). This solution was cooled to -15C and trifluoromethanesulfonic anhydride (triflic anhydride) (0.9 mL, 5.2 mmol) was added dropwise over a period of 25 min under a nitrogen atmosphere with vigorous stirring. The mixture was then allowed to reach room temperature overnight. The reaction mixture was successively washed with ice-cold saturated aqueous NaHCO3(50 mL) and water (50 mL). The organic layer was dried over anhydrous Na2SO4, filtered, and concentrated on a rotary evaporator.2-Tf-O-AcManwas isolated by column chromatography on silica with hexane :EtOAc=1: 1 as the eluant as white solid(1.4 g, 56%).Rfvalue 0.5 (hexane : EtOAc = 1 : 1).
Cyclopropanecarboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
Furan-2-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
Thiophene-2-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
N-[(2S,3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-isonicotinamide[ No CAS ]
N-[(2S,3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-4-dimethylamino-benzamide[ No CAS ]
N-[(2S,3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-4-nitro-benzamide[ No CAS ]
Benzo[b]thiophene-6-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
Naphthalene-2-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
N-[(2S,3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-2-propylsulfanyl-isonicotinamide[ No CAS ]
N-[(2S,3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-4-trifluoromethyl-benzamide[ No CAS ]
3-Chloro-4-(propane-2-sulfonyl)-thiophene-2-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
2-(4-Chloro-phenylsulfanyl)-N-[(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-nicotinamide[ No CAS ]
3-(2-Chloro-6-fluoro-phenyl)-5-methyl-isoxazole-4-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
1-(3,5-Dichloro-phenyl)-5-propyl-1H-pyrazole-4-carboxylic acid [(2S,3R,4R,5S,6R)-4,5-dihydroxy-6-hydroxymethyl-2-((1R,2R,3R,5S)-2,3,5-trihydroxy-5-hydroxymethyl-cyclohexyloxy)-tetrahydro-pyran-3-yl]-amide[ No CAS ]
Acetic acid (2R,3S,4R,6R)-4-acetoxy-2-acetoxymethyl-6-((2R,3S,4S,5R,6S)-3,4,5-trihydroxy-6-methoxy-tetrahydro-pyran-2-ylmethoxy)-tetrahydro-pyran-3-yl ester[ No CAS ]
Acetic acid (2R,3R,4S,5R,6S)-3-acetoxy-2-acetoxymethyl-5-acetylsulfanyl-6-((2R,3R,4S,5R,6S)-4,5-bis-benzyloxy-2-benzyloxymethyl-6-methoxy-tetrahydro-pyran-3-yloxy)-tetrahydro-pyran-4-yl ester[ No CAS ]
With pyridine; trifluoromethanesulfonic acid anhydride; In dichloromethane;
To a solution of mannose tetraacetate 55 (1.50 g. 4.30 mmol) in 46 mL of CH2 Cl2 is added pyridine (1.0 mL, 13 mmol). The solution is cooled to -25 C. and trifluoromethanesulfonic anhydride (1.8 mL, 2.98 g, 10.5 mmol) is added dropwise. The reaction mixture is stirred for 45 min at -25 C. and then diluted with 50 mL of CH2 Cl2, washed with H2 O (100 mL), NaHCO3 (100 mL), saturated NaCl (100 mL), dried over MgSO4, filtered, and concentrated to afford an orange gel. The product is recrystallized from diethyl ether (25 mL) to afford 1.59 g (77%) of 1,3,4,6-tetra-O-acetyl-2-O-trifluoromethanesulfonyl-beta-D-mannopyranose 56 as a white solid: Rf 0.49 (50% EtOAc/hexane); 1 H NMR (CDCl3, 300 MHz) delta 5.92 (s, 1H, H-1), 5.15-5.34 (m, 3H), 4.154.28 (m, 2H), 3.81-3.87 (m, 1H, H-5), 2.08 (s, 3H), 2.10 (s, 3H), 2.12 (s, 3H), 2.16 (s,3H).