Bromoacetonitrile → (S)-cyanomethyl 5-((((2-azidobenzyl)oxy)carbonyl)amino)-2-((tert-butoxycarbonyl)amino)pentanoate

HRID 1482354Notes

Reaction equation

HRID 1482354 reaction equation
[CH:1]([N:4](CC)C(C)C)(C)[CH3:2].BrCC#N.[N:14]([C:17]1[CH:42]=[CH:41][CH:40]=[CH:39][C:18]=1[CH2:19][O:20][C:21]([NH:23][CH2:24][CH2:25][CH2:26][C@H:27]([NH:31][C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[C:28]([OH:30])=[O:29])=[O:22])=[N+:15]=[N-:16]>C(#N)C>[N:14]([C:17]1[CH:42]=[CH:41][CH:40]=[CH:39][C:18]=1[CH2:19][O:20][C:21]([NH:23][CH2:24][CH2:25][CH2:26][C@H:27]([NH:31][C:32]([O:34][C:35]([CH3:38])([CH3:36])[CH3:37])=[O:33])[C:28]([O:30][CH2:2][C:1]#[N:4])=[O:29])=[O:22])=[N+:15]=[N-:16]

Participants

5

Reactant 3

HCID 11534BromoacetonitrileHCID 81531DiisopropylethylamineHCID 89668621(S)-5-((((2-azidobenzyl)oxy)carbonyl)amino)-2-((tert-butoxycarbonyl)amino)pentanoic acid

Product 1

HCID 89668501(S)-cyanomethyl 5-((((2-azidobenzyl)oxy)carbonyl)amino)-2-((tert-butoxycarbonyl)amino)pentanoateYield 100%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

N,N-Diisopropylethylamine (205 μL, 1.176 mmol) and subsequently bromoacetonitrile (373 μL, 5.34 mmol) were added to a solution of (S)-5-((((2-azidobenzyl)oxy)carbonyl)amino)-2-((tert-butoxycarbonyl)amino)pentanoic acid (Compound tk61) (435.5 mg, 1.069 mmol) in acetonitrile (1 mL) at room temperature under a nitrogen atmosphere. The reaction mixture was stirred at the same temperature for 3.5 hours and then concentrated under reduced pressure, and the resulting crude product was purified by normal-phase silica gel column chromatography (hexane/ethyl acetate) to afford (S)-cyanomethyl 5-((((2-azidobenzyl)oxy)carbonyl)amino)-2-((tert-butoxycarbonyl)amino)pentanoate (Compound tk62) (477.2 mg, quant.).

Workup

  1. concentrationconcentrated under reduced pressure
  2. customthe resulting crude product was purified by normal-phase silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-9cec376f72764914b11e778416c41e05
Source dataset
uspto-grants-2016_08
Patent number
US09409952B2

Reaction notes

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