Methanesulfonate → 3-[[1-(Benzoylamino)-3-methylbutyl]methylphenylsilyl]propanoic acid

HRID 2306517

Reaction equation

HRID 2306517 reaction equation
[CH2:1]([Si:5]([CH3:26])([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[CH:6]([NH:11][C:12](=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH2:7][CH:8]([CH3:10])[CH3:9])CC=C.C[C:28]([CH3:30])=[O:29].[OH:31]S(O)(=O)=O.O=[Cr](=O)=O.OS([O-])=O.[Na+].CS([O-])(=O)=O>CC(C)=O.O.O=[Os](=O)(=O)=O.CCCCCC.CCOC(C)=O.CC(O)C>[C:12]([NH:11][CH:6]([Si:5]([CH3:26])([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[CH2:1][CH2:30][C:28]([OH:31])=[O:29])[CH2:7][CH:8]([CH3:10])[CH3:9])(=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

11

Reactant 4

HCID 85257MethanesulfonateHCID 22967188N-[1-[(3-Buten-1-yl)methylphenylsilyl]-3-methyl-1-butyl]benzamideHCID 23665763Sodium BisulfiteHCID 131709961Jones' reagent

Product 1

HCID 229671703-[[1-(Benzoylamino)-3-methylbutyl]methylphenylsilyl]propanoic acid

Reagents, catalysts & solvents 6

HCID 30318Osmium TetroxideCatalystHCID 180AcetoneSolventHCID 962WaterSolvent3×HCID 3776IsopropanolSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 49 (0.7 g, 1.91 mmol) in acetone (22 mL) was added 0.23 mL (2 mol %) of a 4 wt % solution of OsO4 in water and Jones reagent (2.43 mL, 6.49 mmol). After stirring the mixture for 24 h at rt, 2-propanol (0.5 mL) was added followed by NaHSO3 (0.2 g). The mixture was diluted with water (50 mL) and stirred until a dark-green, homogeneous solution was produced. This solution was diluted further with water (90 mL) and extracted with six 50-mL portions of EtOAc. The combined organic extracts were washed with saturated aqueous NaCl and dried over Na2SO4. Concentration gave a colorless solid of crude 50 as a mixture of diastereomers. This product was used in the next reaction without further purification: Rf=0.20 (1/9 EtOAc:hexane); 1H NMR (300 MHz, CDCl3) δ 7.67-7.62 (m, 2H), 7.54-7.52 (m, 2H), 7.48-7.37 (m, 6H), 5.79 and 5.73 (two doublets due to diastereomers, J=10.0 Hz, 1H), 4.25-4.13 (m, 1H), 2.44-2.34 (m, 2H), 1.64-1.57 (m, 1H), 1.49-1.38 (m, 1H), 1.34-1.21 (m, 3H), 1.03, 0.98, 0.90 and 0.84 (four doublets due to diastereomers, J=6.6 Hz, 6H), 0.40 (s, 3H); MS (FAB) m/e (rel. intensity) 384 (MH+, 62), 315 (7), 312 (8), 311 (27), 310 (100), 307 (19), 306 (88), 255 (10), 253 (22); EMS (FAB) calcd for C22H30NO3Si: 384.1995, found: 384.1995.

Workup

  1. stirringstirred until a dark-green, homogeneous solution
  2. customwas produced
  3. extractionextracted with six 50-mL portions of EtOAc
  4. washThe combined organic extracts were washed with saturated aqueous NaCl
  5. dry with materialdried over Na2SO4
  6. concentrationConcentration
  7. customgave a colorless solid of crude 50
  8. additionas a mixture of diastereomers
  9. customThis product was used in the next reaction without further purification

Sources & evidence

ORD record
ord-55650facaa064192b46cb71afe4a46aa
Source dataset
uspto-grants-2002_08
Patent number
US06441212B1

Linked notes

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