2,4-Dichlorobenzaldehyde → (S)-tert-Butyl 3-((2,4-dichlorobenzyl)amino)pyrrolidine-1-carboxylate

HRID 252085

Reaction equation

HRID 252085 reaction equation
C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[C:15]([O:19][C:20]([N:22]1[CH2:26][CH2:25][C@H:24]([NH2:27])[CH2:23]1)=[O:21])([CH3:18])([CH3:17])[CH3:16].[Cl:28][C:29]1[CH:36]=[C:35]([Cl:37])[CH:34]=[CH:33][C:30]=1[CH:31]=O>ClCCCl.ClCCl>[C:15]([O:19][C:20]([N:22]1[CH2:26][CH2:25][C@H:24]([NH:27][CH2:31][C:30]2[CH:33]=[CH:34][C:35]([Cl:37])=[CH:36][C:29]=2[Cl:28])[CH2:23]1)=[O:21])([CH3:18])([CH3:16])[CH3:17]

Participants

6

Reactant 3

HCID 134042,4-DichlorobenzaldehydeHCID 854071tert-butyl (3S)-3-aminopyrrolidine-1-carboxylateHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 66854615(S)-tert-Butyl 3-((2,4-dichlorobenzyl)amino)pyrrolidine-1-carboxylateYield 46.4%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

Alternatively, add sodium triacetoxyborohydride (1.6 g, 7.6 mmol) to a mixture of (S)-3-aminopyrrolidine-1-carboxylic acid tert-butyl ester (1 g, 5.4 mmol) and 2,4-dichlorobenzaldehyde (2.8 g, 16.2 mmol) in 1,2-dichloroethane (10 mL) and stir overnight at room temperature. Dilute with dichloromethane and wash with saturated aqueous sodium chloride, dry (magnesium sulfate) concentrate and chromatograph on silica gel to give (S)-3-(2,4-dichlorobenzylamino)-pyrrolidine-1-carboxylic acid tert-butyl ester (865 mg, 33%). 1H NMR (400 MHz, CDCl3) 7.33-7.38 (2H, m), 7.23 (1H, d, J=7.82 Hz), 3.85 (2H, d, J=1.96 Hz), 3.45-3.56 (2H, m), 3.30-3.40 (2H, m), 3.19-3.10 (1H, m), 2.04 (1H, m), 1.74 (1H, m), 1.46 (9H, s), MS (ES): m/z=345 [M+].

Workup

  1. washwash with saturated aqueous sodium chloride
  2. dry with materialdry (magnesium sulfate)
  3. concentrationconcentrate

Sources & evidence

ORD record
ord-fe6f6a67c45741deb82c820dec456437
Source dataset
uspto-grants-2011_01
Patent number
US07868014B2

Linked notes

Loading…