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4-Methylbenzenethiol → (2R,3R,4S,5S,6R)-2-(acetoxymethyl)-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate

HRID 1862750
Notes
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Reaction equation

HRID 1862750 reaction equation
[C:1]([O:4][C@@H:5]([C@H:8]([C@@H:13]([C@@H:18]([CH2:23][O:24][C:25](=[O:27])[CH3:26])[O:19][C:20](=[O:22])[CH3:21])[O:14][C:15](=[O:17])[CH3:16])[O:9][C:10](=O)C)C=O)(=[O:3])[CH3:2].[CH3:28][C:29]1[CH:34]=[CH:33][C:32]([SH:35])=[CH:31][CH:30]=1.B(F)(F)F.CCOCC>C(Cl)Cl>[C:25]([O:24][C@H:23]1[C@@H:18]([O:19][C:20](=[O:22])[CH3:21])[C@H:13]([O:14][C:15](=[O:17])[CH3:16])[C@@H:8]([CH2:5][O:4][C:1](=[O:3])[CH3:2])[O:9][C@@H:10]1[S:35][C:32]1[CH:33]=[CH:34][C:29]([CH3:28])=[CH:30][CH:31]=1)(=[O:27])[CH3:26]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 78114-MethylbenzenethiolHCID 8000Boron trifluoride etherateHCID 11383716Mannose pentaacetate

Product 1

HCID 11775389(2R,3R,4S,5S,6R)-2-(acetoxymethyl)-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetateYield 87%

Reagents, catalysts & solvents 1

HCID 6344Dichloromethane
Solvent
2×

Procedure

To a mixture of D-mannose pentaacetate (16.0 g, 0.041 mol) and p-thiocresol (7.6 g, 0.0615 mol) in CH2Cl2 (200 mL), boron trifluoride diethyl etherate (6.8 mL, 0.0533 mol) was added. The mixture was stirred overnight. The reaction mixture was then diluted with CH2Cl2 (200 mL), washed with sat. NaHCO3 (2×120 mL) and water (100 mL). The organic layer was dried over Na2SO4. The solvent was removed, and the residue was purified by column chromotography on silia gel (hexanes/EtOAc 3:1) to give product (16.2 g, 87%) as a syrup: 1HNMR (500 MHz, CDCl3), δ 7.38 (d, J=8.0 Hz, 2H), 7.12 (d, J=8.0 Hz, 2H), 5.49 (dd, 1H, J=2.5, 1.5 Hz), 5.42 (d, 1H, J=1.0 Hz), 5.30-5.35 (m, 2H), 4.54-4.58 (m, 1H), 4.30 (dd, 1H, J=12.5, 6.0 Hz), 4.11 , (dd, 1H, J=12.0, 2.5 Hz), 2.33 (s, 3H), 2.15 (s, 3H), 2.08 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H); HRMS (M+Cs) calcd for C21H26O9SCs 587.0352, found 587.0331.

Workup

  1. additionwas added
  2. washwashed with sat. NaHCO3 (2×120 mL) and water (100 mL)
  3. dry with materialThe organic layer was dried over Na2SO4
  4. customThe solvent was removed
  5. customthe residue was purified by column chromotography on silia gel (hexanes/EtOAc 3:1)

Sources & evidence

ORD record
ord-6bc9f2966c884d38a4b2214f0713ac19
Source dataset
uspto-grants-2003_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06538117B1

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes