Benzoyl chloride → HCID 71152508, compound

HRID 1497286Notes

Reaction equation

HRID 1497286 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[C@@H:19]([OH:20])[C@H:18]([OH:21])[C@H:13]2[NH:14][C:15](=[O:17])[O:16][C@H:12]2[CH2:11]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[C:22](Cl)(=[O:29])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1>CN(C)C1C=CN=CC=1.N1C=CC=CC=1.CCOC(C)=O>[C:22]([O:21][C@@H:18]1[C@H:13]2[NH:14][C:15](=[O:17])[O:16][C@H:12]2[CH2:11][C@H:10]([CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:3])[CH3:2])[C@H:19]1[O:20][C:9](=[O:8])[C:10]1[CH:19]=[CH:18][CH:13]=[CH:12][CH:11]=1)(=[O:29])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

6

Reactant 2

HCID 7412Benzoyl chlorideHCID 71153437HCID 71153437, compound

Product 1

HCID 71152508HCID 71152508, compoundYield 178.8%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (3aR,4R,5R,6R,7aS)-6-(((tert-butyldimethylsilyl)oxy)methyl)-4,5-dihydroxyhexahydrobenzo[d]oxazol-2(3H)-one (2.21 g, 7.00 mmol) and 4-dimethylaminopyridine (30 mg, 0.24 mmol) in pyridine (20 mL) at 0° C. was added benzoyl chloride (3.92 g, 27.9 mmol) dropwise. The mixture was stirred at room temperature for 20 h. The reaction was diluted with EtOAc (300 mL), washed with saturated aqueous NaHCO3 water (2×150 mL), 0.5 N HCl (2×100 mL) and brine and dried over MgSO4. The solvent was evaporated to give the crude product. This was purified by basic alumina column, eluted with 10-30% EtOAc in hexanes to provide (3aS,4R,5R,6R,7aS)-6-(((tert-butyldimethylsilyl)oxy)methyl)-2-oxooctahydrobenzo[d]oxazole-4,5-diyl dibenzoate (3.29 g, 90%). 1H NMR (400 MHz, CDCl3) δ 7.92-7.97 (m, 4H), 7.49-7.53 (m, 2H), 7.35-7.39 (m, 4H), 6.07 (s, 1H), 5.53 (t, J=10.1 Hz, 1H), 5.13 (dd, J=9.6 Hz, 6.6 Hz, 1H), 4.91-4.94 (m, 1H), 3.89 (t, J=7.0 Hz, 1H), 3.79 (dd, J=10.0 Hz, 4.0 Hz, 1H), 3.61 (dd, J=10.0 Hz, 2.6 Hz, 1H), 2.40 (dt, J=15.5 Hz, 3.0 Hz, 1H), 2.27-2.36 (m, 1H), 2.03-2.11 (m, 1H), 0.87 (s, 9H), −0.03 (s, 3H), −0.07 (s, 3H).

Workup

  1. washwashed with saturated aqueous NaHCO3 water (2×150 mL), 0.5 N HCl (2×100 mL) and brine
  2. dry with materialdried over MgSO4
  3. customThe solvent was evaporated
  4. customto give the crude product
  5. customThis was purified by basic alumina column
  6. washeluted with 10-30% EtOAc in hexanes

Sources & evidence

ORD record
ord-883448eba5664571acc0ba37c07b9d36
Source dataset
uspto-grants-2015_12
Patent number
US09199949B2

Reaction notes

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