Methyl Acetate → HCID 68731966, compound

HRID 1523231Notes

Reaction equation

HRID 1523231 reaction equation
N(C(C)C)C(C)C.[Li]CCCC.[C:13]([O:16][CH3:17])(=[O:15])[CH3:14].[CH3:18][C:19]([S@@:22]([N:24]=[C:25]([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[CH3:26])=[O:23])([CH3:21])[CH3:20]>C1COCC1>[CH3:21][C:19]([CH3:18])([S@@:22]([NH:24][C@:25]([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)([CH3:26])[CH2:14][C:13]([O:16][CH3:17])=[O:15])=[O:23])[CH3:20]

Participants

6

Reactant 4

HCID 6584Methyl AcetateHCID 7912DiisopropylamineHCID 86649302HCID 86649302, compoundHCID 178418339Butyllithium

Product 1

HCID 68731966HCID 68731966, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of i-Pr2NH in THF (25 mL) was cooled to −78° C., n-BuLi (2.5M, 2 mL) was added and the solution was stirred for 1 h. Then methyl acetate (4.48 mmol, 278 mg) was added and the mixture was stirred for 30 min. To this solution Ti(Oi-Pr)3Cl (1 M, 9.4 mL) was added. After 0.5 h, (S)-2-methyl-N-(1-phenylethylidene)propane-2-sulfinamide (500 mg, 2.24 mmol) dissolved in THF (1 mL) was added. The mixture was stirred at −78° C. for 3 h. The reaction was quenched with NH4Cl and warmed to rt. The mixture was diluted with water and filtered. The solid was washed with H2O/EtOAc and filtered. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated. The residue was purified by preparative TLC to afford (R)-methyl 3-((S)-1,1-dimethylethylsulfinamido)-3-phenylbutanoate (305 mg, 46%). 1H NMR (CDCl3): 1.24 (s, 9H), 1.68 (s, 3H), 3.08 (s, 2H), 3.53 (s, 3H), 5.46 (s, 1H), 7.15-7.18 (m, 1H), 7.23-7.30 (m, 2H), 7.30-7.36 (m, 2H).

Workup

  1. stirringthe mixture was stirred for 30 min
  2. waitAfter 0.5 h
  3. additionwas added
  4. stirringThe mixture was stirred at −78° C. for 3 h
  5. customThe reaction was quenched with NH4Cl
  6. additionThe mixture was diluted with water
  7. filtrationfiltered
  8. washThe solid was washed with H2O/EtOAc
  9. filtrationfiltered
  10. washThe combined organic layers were washed with brine
  11. dry with materialdried over Na2SO4
  12. concentrationconcentrated
  13. customThe residue was purified by preparative TLC

Sources & evidence

ORD record
ord-1097d4c56598437eba6e96256339d1c9
Source dataset
uspto-grants-2015_07
Patent number
US09079861B2

Reaction notes

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