tert-Butylsulfinamide, (R)-(+)- → tert-butyl N-[(1S)-1-(4-bromophenyl)ethyl]-N-[(4E)-4-[(R)-tert-butylsulfinyl]imino-4-phenylbutyl]carbamate

HRID 219611Notes

Reaction equation

HRID 219611 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C@@H:8]([N:10]([CH2:18][CH2:19][CH2:20][C:21](=O)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH3:9])=[CH:4][CH:3]=1.[C:29]([S@:33]([NH2:35])=[O:34])([CH3:32])([CH3:31])[CH3:30]>C1COCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C@@H:8]([N:10]([CH2:18][CH2:19][CH2:20]/[C:21](=[N:35]\[S@@:33]([C:29]([CH3:32])([CH3:31])[CH3:30])=[O:34])/[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH3:9])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 59190380(S)-tert-butyl 1-(4-bromophenyl)ethyl(4-oxo-4-phenylbutyl)carbamate

Product 1

HCID 88542676tert-butyl N-[(1S)-1-(4-bromophenyl)ethyl]-N-[(4E)-4-[(R)-tert-butylsulfinyl]imino-4-phenylbutyl]carbamateYield 51%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

(S)-tert-butyl 1-(4-bromophenyl)ethyl(4-oxo-4-phenylbutyl)carbamate (3.14 g, 7.04 mmol), (R)-t-Butylsulfinamide, Ti(OEt)4 (125 μL, 1.5 equiv) were mixed with dry THF (80 mL) and heated at reflux for overnight. LC-MS found most of starting material was consumed. The mixture was diluted with ether (200 mL), washed with water (50 mL), brine (30 mL), dried over Na2SO4. After filtration and concentration, the residue was purified by chromatography on a 120-g silica gel cartridge, eluted with a 10˜35% EtOAc in hexanes gradient, to afford tert-butyl (S)-1-(4-bromophenyl)ethyl((E)-4-((R)-tert-butylsulfinylimino)-4-phenylbutyl)carbamate (1.97 g, 51%) product and recovered starting material (0.72 g). LC-MS Method 1 tR=2.43 min, m/z 549, 551 (M+1)

Workup

  1. temperatureheated
  2. temperatureat reflux for overnight
  3. customwas consumed
  4. additionThe mixture was diluted with ether (200 mL)
  5. washwashed with water (50 mL), brine (30 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationAfter filtration and concentration
  8. customthe residue was purified by chromatography on a 120-g silica gel cartridge
  9. washeluted with a 10˜35% EtOAc in hexanes gradient

Sources & evidence

ORD record
ord-a06e3981d2844da3a2bf0330af91f491
Source dataset
uspto-grants-2012_06
Patent number
US08202857B2

Reaction notes

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