Methanol → HCID 15734879, compound

HRID 1199274Notes

Reaction equation

HRID 1199274 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@@H:13]([CH2:32][O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[O:12][C:10]1([CH:41]([S:44][CH3:45])[S:42][CH3:43])[OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].CO.C(Cl)(Cl)Cl>O1CCCC1>[CH2:1]([O:8][C@H:9]([C@H:15]([C@@H:14]([C@@H:13]([CH2:32][O:33][CH2:34][C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)[OH:12])[O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[O:16][CH2:17][C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[CH:10]([CH:41]([S:44][CH3:45])[S:42][CH3:43])[OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 6212Chloroform2×HCID 21226445Aluminium lithium hydrideHCID 54523007HCID 54523007, compound

Product 1

HCID 15734879HCID 15734879, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

2,3,4,6-Tetra-O-benzyl-1-C-[bis(methylthio)methyl]-D-glucopyranose (4.0 g) was dissolved in tetrahydrofuran (140 mL), to which lithium aluminum hydride (2.8 g) was added in portions under ice-cooling, and stirred at the same temperature for 18 hours and then at room temperature for 3 hours. Methanol (50 mL) was added dropwise to the mixture under ice-cooling, and evaporated under reduced pressure. The residue was added to a mixture of ethyl acetate (200 mL) and water (200 mL) under ice-cooling, and acidified (pH 1) with 2N hydrochloric acid under stirring. The ethyl acetate layer was separated and the aqueous layer was extracted with ethyl acetate (200 mL). The ethyl acetate extracts were combined, washed with water and saturated sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and evaporate under reduced pressure. The residue was chromatographed on a column of silica gel (500 mL) with toluene-ethyl acetate (6:1) to resolve the two isomers, i.e. (1R)- and (1S)-isomers of 2,3,4,6-tetra-O-benzyl-1-C-[bis(methylthio)methyl]-D-glucitol. The fraction eluted earlier (550- 900 mL) was evaporated to dryness under reduced pressure, to give an isomer (11.5 g) showing [α]25D -5.8° (c=1, CHCl3) as a colorless syrup, and the fraction eluted later (1.1-1.8 L) was evaporated to dryness under reduced pressure to give an isomer (0.9 g) showing [α]25D -12.7° (c=1, CHCl3) as a colorless syrup. The isomer eluted earlier: NMR (CDCl3) δ: 2.12 (6H, s, CH3S--×2), 2.84 (1H, d, J=5.2 Hz, 5--OH), 3.44 (1H, dd, J=0.5 Hz, 2.6 Hz, 1--OH), 3.62 (2H, d, J=4.8 Hz, 6--CH2), 3.85 (1H, dd, J=0.5 Hz, 2.7Hz, (MeS)2CH--), 3.93 (1H, dd, J=3.5 Hz, 6.2 Hz, 4--CH), 4.03 (1H, t*, J=3.5 Hz, 4.2 Hz, 3--CH), 4.05-4.10 (1H, m, 5--CH), 4.15 (1H, dd, J=4.2 Hz, 8.3 Hz, 2--CH), 4,23 (1H, td*, J=2.6 Hz, 2.7 Hz, 8.3 Hz, 1--CH); 4.50 (1H, d, J=11.9 Hz), 4.55 (1H, d, J=11.9 Hz), 4.58 (1H, d, J=11.5 Hz), 4.60 (1H, d, J=11.2 Hz), 4.61 (1H, d, J=11.2 Hz), 4.63 (1H, d, J=11.5 Hz), 4.65 (1H, d, J=11.2 Hz) and 4.71 (1H, d, J=11.2 Hz)(PhCH2 --×4); 7.24-7.38 (20H, m, C6H5 --×4)(* apparent splitting pattern). Elemental analysis for C37H44O6S2 : Calc.(%): C, 68.49; H, 6.83; S, 9.88. Found(%): C, 68.78; H, 6.92; S, 9.76. The isomer eluted later: NMR (CDCl3) δ: 1.97 (3H, s, CH3S--), 1.99 (3H, s, CH3S--), 2.96 (1H, d, J=5.2 Hz, --OH), 3.05 (1H, d, J=5.1 Hz, --OH), 3.58-3.69 (3H, m, 1--CH, 6--CH2), 3.73 (1H, dd, J=3.0 Hz, 6.9 Hz, 4--CH), 3.80 (1H, d, J=9.1 Hz, (MeS)2CH--), 4.08-4.15 (1H, m, 5--CH), 4.18 (1H, dd, J=3.0 Hz, 8.3 Hz, 3--CH), 4.37 (1H, dd, J=1.5 Hz, 8.3 Hz, 2--CH); 4.50 (1H, d, J=11.9 Hz), 4.55 (1H, d, J=11.9 Hz), 4.57 (1H, d, J= 11.5 Hz), 4.61 (1H, d, J=11.5 Hz), 4.68 (1H,dd, J=11.3 Hz), 4.73 (1H, d, J=11.4 Hz), 4.82(1H, d, J=11.3 Hz) and 4.94 (1H, d, J=11.4 Hz)(PhCH2 --×4); 7.25-7.34 (20H, m, C6H5 --×4). Elemental analysis for C37H44O6S2 : Calc.(%): C, 68.49; H, 6.83; S, 9.88. Found(%): C, 68.82; H, 6.99; S, 9.58.

Workup

  1. additionwas added in portions under ice-
  2. temperaturecooling
  3. waitat room temperature for 3 hours
  4. temperaturecooling
  5. customevaporated under reduced pressure
  6. additionThe residue was added to a mixture of ethyl acetate (200 mL) and water (200 mL) under ice-
  7. temperaturecooling
  8. stirringunder stirring
  9. customThe ethyl acetate layer was separated
  10. extractionthe aqueous layer was extracted with ethyl acetate (200 mL)
  11. washwashed with water and saturated sodium hydrogencarbonate solution
  12. dry with materialdried over anhydrous sodium sulfate
  13. customevaporate under reduced pressure
  14. customThe residue was chromatographed on a column of silica gel (500 mL) with toluene-ethyl acetate (6:1)
  15. washThe fraction eluted earlier (550- 900 mL)
  16. customwas evaporated to dryness under reduced pressure
  17. customto give an isomer (11.5 g)
  18. washthe fraction eluted later (1.1-1.8 L)
  19. customwas evaporated to dryness under reduced pressure
  20. customto give an isomer (0.9 g)
  21. washThe isomer eluted earlier
  22. washThe isomer eluted later

Sources & evidence

ORD record
ord-5c4ec42b49da46b88542c41e52195270
Source dataset
uspto-grants-1990_02
Patent number
US04898986

Reaction notes

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