Ammonium Chloride → Ethyl 4-([1,1'-biphenyl]-2-yl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate

HRID 594354Notes

Reaction equation

HRID 594354 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.[Li]CCCC.[C:19]([S:23]([N:25]=[CH:26][CH2:27][CH:28]([CH3:34])[C:29]([O:31][CH2:32][CH3:33])=[O:30])=[O:24])([CH3:22])([CH3:21])[CH3:20].[NH4+].[Cl-]>C1COCC1.O.CCOCC>[C:3]1([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[CH:26]([NH:25][S:23]([C:19]([CH3:21])([CH3:20])[CH3:22])=[O:24])[CH2:27][CH:28]([CH3:34])[C:29]([O:31][CH2:32][CH3:33])=[O:30]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 750251,1'-Biphenyl, 2-iodo-HCID 86695624Ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoateHCID 178418339Butyllithium

Product 1

HCID 86695627Ethyl 4-([1,1'-biphenyl]-2-yl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A cooled (−78° C.) solution of commercially available 2-iodo-1,1′-biphenyl (680 mg; 2.43 mmol) in anh. THF (20 ml), under nitrogen, was treated dropwise with a solution of 1.6 M n-BuLi in hexanes (1.52 ml; 2.43 mmol). The resulting solution was further stirred at −78° C. for 10 min. A solution of ethyl 4-((tert-butylsulfinyl)imino)-2-methylbutanoate (600 mg; 2.43 mmol) in anh. THF (5 ml) was added to the cooled reaction mixture, and stirring was continued from −78° C. to 0° C. over 1 h. The resulting reaction mixture was treated successively with aq. sat. NH4Cl (80 ml), Et2O (250 ml) and water (75 ml). The separated organic layer was then washed with brine (75 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=25/1) afforded ethyl 4-([1,1′-biphenyl]-2-yl)-4-(1,1-dimethylethylsulfinamido)-2-methylbutanoate as a mixture of stereoisomers. LC-MS (conditions A): tR=0.93 min.; [M+H]+: 401.79 g/mol and tR=0.94 min.; [M+H]+: 401.80 g/mol.

Workup

  1. stirringstirring
  2. waitwas continued from −78° C. to 0° C. over 1 h
  3. customThe resulting reaction mixture
  4. washThe separated organic layer was then washed with brine (75 ml)
  5. dry with materialdried over anh. MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure
  8. customPurification by FC (DCM/MeOH=25/1)

Sources & evidence

ORD record
ord-0c7c69b30ca541d0b2616f5e0b8a8fda
Source dataset
uspto-grants-2016_01
Patent number
US09242970B2

Reaction notes

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