Dimethyl Sulfoxide → HCID 59201395, compound

HRID 451808Notes

Reaction equation

HRID 451808 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([O:15][C:16]([NH:18][C@@H:19]([CH2:24][CH:25]1[CH2:30][CH2:29][CH:28]([OH:31])[CH2:27][CH2:26]1)[C:20]([O:22][CH3:23])=[O:21])=[O:17])([CH3:14])([CH3:13])[CH3:12].C([O-])(O)=O.[Na+]>C(Cl)Cl.CCN(CC)CC>[C:11]([O:15][C:16]([NH:18][C@@H:19]([CH2:24][CH:25]1[CH2:30][CH2:29][C:28](=[O:31])[CH2:27][CH2:26]1)[C:20]([O:22][CH3:23])=[O:21])=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 516892Sodium BicarbonateHCID 59383042HCID 59383042, compound

Product 1

HCID 59201395HCID 59201395, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 8471TriethylamineSolvent

Conditions

Temperature
-40 °C

Procedure

To a solution of oxalyl dichloride (49.5 g, 0.39 mol) in dry CH2Cl2 (480 mL) was added dropwise a solution of dry DMSO (60.8 g, 0.78 mol) in dry CH2Cl2 (200 mL) at −65° C. for about 0.5-1 hr. Then a solution of (S)-methyl 2-(tert-butoxycarbonylamino)-3-(4-hydroxycyclohexyl)propanoate (59.5 g, 0.197 mol) in dry CH2Cl2 (600 mL) was added dropwise to the above mixture for about 0.5-1 hr. It was allowed to stir for 4-6 hr at −50-−30° C. Upon completion of the reaction, 158 mL of Et3N was added dropwise and the mixture was warmed to rt. The solution was added sat. NaHCO3, extracted by EtOAc, washed with H2O, brine, dried over Na2SO4, filtered and concentrated. The residue was purified by flash chromatograph to give (S)-methyl 2-(tert-butoxycarbonylamino)-3-(4-oxocyclohexyl)propanoate (39.5 g, 67%). 1H NMR (CDCl3, 400 MHz) δ 5.00 (d, J=8.0H, 1H), 4.39 (m, 1H), 3.74 (s, 3H), 2.40-1.30 (m, 11H), 1.44 (s, 9H). MS ESI +ve m/z 301 (M+1).

Workup

  1. additionwas added dropwise
  2. temperaturethe mixture was warmed to rt
  3. extractionextracted by EtOAc
  4. washwashed with H2O, brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatograph

Sources & evidence

ORD record
ord-d088f61a62424dbeb9680705b5787fc1
Source dataset
uspto-grants-2013_07
Patent number
US08487108B2

Reaction notes

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