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

HRID 252085
Notes
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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]
ParticipantsProcedureWorkupSources & evidenceReaction notes

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-Dichloroethane
Solvent
HCID 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
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07868014B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes