Thiophenol → HCID 53919941, compound

HRID 1637432Notes

Reaction equation

HRID 1637432 reaction equation
C(O[C@@H:8]1[O:34][C@H:33]([CH2:35][O:36][C:37](=[O:42])[C:38]([CH3:41])([CH3:40])[CH3:39])[C@@H:25]([O:26][C:27](=[O:32])[C:28]([CH3:31])([CH3:30])[CH3:29])[C@H:17]([O:18][C:19](=[O:24])[C:20]([CH3:23])([CH3:22])[CH3:21])[C@H:9]1[O:10][C:11](=[O:16])[C:12]([CH3:15])([CH3:14])[CH3:13])(=O)C(C)(C)C.[C:43]1([SH:49])[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1>C(Cl)Cl>[C:43]1([S:49][C@@H:8]2[O:34][C@H:33]([CH2:35][O:36][C:37](=[O:42])[C:38]([CH3:41])([CH3:40])[CH3:39])[C@@H:25]([O:26][C:27](=[O:32])[C:28]([CH3:29])([CH3:30])[CH3:31])[C@H:17]([O:18][C:19](=[O:24])[C:20]([CH3:21])([CH3:22])[CH3:23])[C@H:9]2[O:10][C:11](=[O:16])[C:12]([CH3:15])([CH3:13])[CH3:14])[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1

Participants

4

Reactant 2

HCID 7969ThiophenolHCID 10941025HCID 10941025, compound

Product 1

HCID 53919941HCID 53919941, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 43 (1.49 g, 2.49 mmol) in 50 mL CH2Cl2 is added thiophenol (0.64 mL, 686 mg, 6.22 mmol) followed by boron trifluoride diethyl ether complex (1.53 mL, 1.76 g, 12.45 mmol). The reaction mixture is stirred at room temperature for 4 h and quenched by the slow addition of 10 mL saturated NaHCO3 solution. The reaction mixture is diluted with 100 mL of CH2Cl2, washed with H2O (100 mL), saturated NaCl (100 mL), dried over Na2SO4, filtered, concentrated and purified by flash chromatography (5% EtOAc/hexane) to afford 1.24 g (82%) of 1-deoxy-1-(phenylthio)-2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranose 44: Rf 0.25 (5% EtOAc/hexane); 1H NMR (CDCl3, 270 MHz) δ 7.47-7.50 (m, 2H), 7.22-7.30 (m, 3H), 5.34 (app t, J=9.4 Hz, 1H, H-3), 5.08 (app t, J=9.7 Hz, 1H, H-4), 5.03 (app t, J=9.7 Hz, 1H, H-2), 4.73 (d, J=9.8 Hz, 1H, H-1), 4.25 (dd, J=12.2, 1.6 Hz, 1H, H-6), 4.04 (dd, J=12.2, 5.9 Hz, 1H, H-6), 3.76 (ddd, J=10.2, 5.9, 1.6 Hz, 1H, H-5), 1.21 (s, 9H), 1.20 (s, 9H), 1.14 (s, 9H), 1.10 (s, 9H); 13C NMR (CDCl3, 68 MHz) δ 177.8, 176.9, 176.2, 176.1, 132.5, 132.2, 129.2, 129.1, 128.1. 128.8, 86.4, 76.3, 73.1, 69.3, 67.5, 62.1, 38.7, 38.6, 27.4, 27.0, 29.9; FABMS C32H48O9S (MNa+) calcd 631.2917, found 631.2943.

Workup

  1. customquenched by the slow addition of 10 mL saturated NaHCO3 solution
  2. additionThe reaction mixture is diluted with 100 mL of CH2Cl2
  3. washwashed with H2O (100 mL), saturated NaCl (100 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified by flash chromatography (5% EtOAc/hexane)

Sources & evidence

ORD record
ord-42697b60c3c94568842cc5807d60e9be
Source dataset
uspto-grants-2000_03
Patent number
US06040433

Reaction notes

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