Water → (2R,3S,4S,5R,6S)-3,4,5-tris(Benzyloxy)-2-((benzyloxy)methyl)-6-(p-tolylthio)tetrahydro-2H-pyran

HRID 1745924Notes

Reaction equation

HRID 1745924 reaction equation
[S:1]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)[C@@H:2]1[O:10][C@H:9]([CH2:11][OH:12])[C@H:7]([OH:8])[C@H:5]([OH:6])[C@H:3]1[OH:4].[H-].[Na+].[CH:22]1[CH:27]=[CH:26][C:25]([CH2:28]Br)=[CH:24][CH:23]=1.O>CN(C=O)C>[CH2:28]([O:4][C@@H:3]1[C@@H:5]([O:6][CH2:28][C:25]2[CH:26]=[CH:27][CH:22]=[CH:23][CH:24]=2)[C@@H:7]([O:8][CH2:28][C:25]2[CH:26]=[CH:27][CH:22]=[CH:23][CH:24]=2)[C@@H:9]([CH2:11][O:12][CH2:19][C:16]2[CH:17]=[CH:18][CH:13]=[CH:14][CH:15]=2)[O:10][C@H:2]1[S:1][C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)[C:25]1[CH:26]=[CH:27][CH:22]=[CH:23][CH:24]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 7315241(2R,3R,4S,5R,6S)-2-(Hydroxymethyl)-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triol

Product 1

HCID 11050551(2R,3S,4S,5R,6S)-3,4,5-tris(Benzyloxy)-2-((benzyloxy)methyl)-6-(p-tolylthio)tetrahydro-2H-pyranYield 177.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
-10 °C

Procedure

p-Methylphenyl 1-thio-β-D-galactopyranoside (1.0 g, 3.5 mmol) was dissolved in dry DMF (15 mL) and cooled to −10° C. At this temperature (840 mg, 35 mmol) NaH was added and the mixture allowed to warm up to rt. and stirred for an additional 10 min. Then BnBr (4.1 mL, 35 mmol) was added, and the mixture was stirred for 5 h. At 0° C. 10 mL H2O was added and the mixture extracted with EtOAc (3×50 mL). The organic layer was dried over MgSO4 and evaporated to dryness. Flash chromatography using Hexane/EtOAc (5:1) gave the title compound as a white solid (2.01 g, 89%). [α]D22 −1.2° (c, 0.5, CHCl3); 1H-NMR (400 MHz, CDCl3), δ 2.27 (s, 3H), 3.56–3.65 (m, 4H), 3.89 (t, 1H, J=9.4 Hz) 3.97 (s, 1H), 4.42 (ABq, 2H, J=11.6 Hz), 4.594.60 (m, 3H), 4.70 (m, 3H), 4.73 (ABq, 2H, J=10.1 Hz), 4.95 (d, 1H, J=11.5 Hz), 6.98 (d, 2H, J=8.6 Hz), 7.25–7.47 (m, 22H); 13C-NMR (400 MHz, CDCl3), δ 21.04, 68.68, 72.63, 73.48, 74.34, 75.54, 77.16, 77.24, 84.13, 87.95, 127.36, 127.49, 127.60, 127.65, 127.71, 127.78, 127.86, 128.09, 128.26, 128.35, 129.49, 132.10; HRMS (M+Cs) calcd for C41H42O5SCs 779.1807. found 779.1782.

Workup

  1. temperatureto warm up to rt
  2. stirringthe mixture was stirred for 5 h
  3. customAt 0° C
  4. extractionthe mixture extracted with EtOAc (3×50 mL)
  5. dry with materialThe organic layer was dried over MgSO4
  6. customevaporated to dryness

Sources & evidence

ORD record
ord-2f24a6bdf287497c9aa75b042c148ca0
Source dataset
uspto-grants-2006_03
Patent number
US07019131B2

Reaction notes

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