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

HRID 1745925Notes

Reaction equation

HRID 1745925 reaction equation
[C:1]([O:4][C@H:5]1[C@H:18]([O:19][C:20](=O)[CH3:21])[C@H:17]([O:23][C:24](=O)[CH3:25])[C@H:16]([CH3:27])[O:15][C@@H:6]1[S:7][C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1)(=O)[CH3:2].C[O-].[Na+].CO.[H-].[Na+].[CH:35]1[CH:40]=[CH:39][C:38]([CH2:41]Br)=CC=1>CN(C=O)C.O.CCCCCC>[CH2:1]([O:4][C@H:5]1[C@H:18]([O:19][CH2:20][C:21]2[CH:5]=[CH:18][CH:17]=[CH:16][CH:27]=2)[C@H:17]([O:23][CH2:24][C:25]2[CH:41]=[CH:38][CH:39]=[CH:40][CH:35]=2)[C@H:16]([CH3:27])[O:15][C@@H:6]1[S:7][C:8]1[CH:9]=[CH:10][C:11]([CH3:14])=[CH:12][CH:13]=1)[C:2]1[CH:12]=[CH:13][CH:8]=[CH:9][CH:10]=1

Participants

8

Reactant 4

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 10000824HCID 10000824, compoundHCID 23694274Sodium methanolate methanol

Product 1

HCID 11071610(2S,3R,4R,5S,6R)-3,4,5-tris(benzyloxy)-2-methyl-6-(p-tolylthio)tetrahydro-2H-pyranYield 152.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8058HexaneSolvent

Procedure

p-Methylphenyl 2,3,4-Tri-O-acetyl-1-thio-β-L-fucopyranoside (ibid, Brukart, M. D. et al. 1997) (2.5 g, 6.31 mmol) was treated with NaOMe-MeOH. The product was further treated with 85% NaH (463 g, 22.7 mmol) and BnBr (5.8 mL, 37.86 mmol) in DMF (25 mL). After reaction was finished, hexane (30 mL) and water (300 mL) were added into the vigorously stirred solution. The solid product was filtered, washed with water (2×5 mL) and hexane-AcOEt (15:1, 2×5 mL). The crude product was suspended in a hot (70° C.) mixture of AcOEt-Hexane (10:1), and stirred for 10 min, cooled to rt, filtered to gave pure 50 (2.6 g, 76%) as solid: [α]D22 +8° (c, 0.5, CHCl3); HRMS (M+Cs) calcd for C34H36O4SCs 672.1290. found 672.1287.

Workup

  1. customAfter reaction
  2. filtrationThe solid product was filtered
  3. washwashed with water (2×5 mL) and hexane-AcOEt (15:1, 2×5 mL)
  4. additionThe crude product was suspended in a hot (70° C.) mixture of AcOEt-Hexane (10:1)
  5. filtrationfiltered

Sources & evidence

ORD record
ord-03486b7808ee4e40bf5e2ff89503d728
Source dataset
uspto-grants-2006_03
Patent number
US07019131B2

Reaction notes

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