Borane → (R)-N-(4-chloro-3-(phenylthio)benzyl)-1-(3-chlorophenyl)ethanamine

HRID 1801576Notes

Reaction equation

HRID 1801576 reaction equation
[Cl:1][C:2]1[CH:19]=[CH:18][C:5]([C:6]([NH:8][C@@H:9]([C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([Cl:17])[CH:12]=2)[CH3:10])=O)=[CH:4][C:3]=1[S:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.B>C1COCC1>[Cl:1][C:2]1[CH:19]=[CH:18][C:5]([CH2:6][NH:8][C@@H:9]([C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([Cl:17])[CH:12]=2)[CH3:10])=[CH:4][C:3]=1[S:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

4

Reactant 2

HCID 6331BoraneHCID 59803178(R)-4-chloro-N-(1-(3-chlorophenyl)ethyl)-3-(phenylthio)benzamide

Product 1

HCID 24953404(R)-N-(4-chloro-3-(phenylthio)benzyl)-1-(3-chlorophenyl)ethanamineYield 45%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (R)-4-chloro-N-(1-(3-chlorophenyl)ethyl)-3-(phenylthio)benzamide 33 (0.631 g, 1.57 mmol) in THF (8 mL) was added borane (0.110 g, 7.95 mmol) (8 mL, 1 M in THF). The reaction mixture was heated to reflux for 2 d, quenched with 1 M NaOH, and diluted with EtOAc. The organic phase was washed with water (1×), brine (1×), dried over MgSO4, filtered, and concentrated in vacuo. Purification by flash column chromatography on silica gel (eluted with 20% to 50% EtOAc in hexanes) gave (R)—N-(4-chloro-3-(phenylthio)benzyl)-1-(3-chlorophenyl)ethanamine 34 (0.274 g, 45.0% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 1.26 (d, J=6.5 Hz, 3H), 3.41 (d, J=13.7 Hz, 1H), 3.50 (d, J=13.7 Hz, 1H), 3.65 (q, J=6.7 Hz, 3H), 6.93 (s, 1H), 7.05-7.09 (m, 2H), 7.20-7.25 (m, 2H), 7.37-7.43 (m, 6H). Mass spectrum: calculated for C15H14Cl2NS 387.1. found 388.1 (M++1).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 2 d
  3. customquenched with 1 M NaOH
  4. additiondiluted with EtOAc
  5. washThe organic phase was washed with water (1×), brine (1×)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification by flash column chromatography on silica gel (eluted with 20% to 50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-4522dad1860b4b16ba6ba0c23f9892df
Source dataset
uspto-grants-2013_01
Patent number
US08349831B2

Reaction notes

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