Benzyl chloroformate → Methyl 2-(2-(((benzyloxy)carbonyl)amino)pent-4-ynamido)-4-methylpentanoate

HRID 627578Notes

Reaction equation

HRID 627578 reaction equation
[Cl-].[CH3:2][O:3][C:4](=[O:18])[CH:5]([NH:10][C:11](=[O:17])[CH:12]([NH3+:16])[CH2:13][C:14]#[CH:15])[CH2:6][CH:7]([CH3:9])[CH3:8].CCN(C(C)C)C(C)C.[CH2:28]([O:35][C:36](Cl)=[O:37])[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>C1COCC1>[CH2:28]([O:35][C:36]([NH:16][CH:12]([CH2:13][C:14]#[CH:15])[C:11]([NH:10][CH:5]([CH2:6][CH:7]([CH3:9])[CH3:8])[C:4]([O:3][CH3:2])=[O:18])=[O:17])=[O:37])[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformateHCID 81531DiisopropylethylamineHCID 900103681-((1-Methoxy-4-methyl-1-oxopentan-2-yl)amino)-1-oxopent-4-yn-2-aminium chloride

Product 1

HCID 78106115Methyl 2-(2-(((benzyloxy)carbonyl)amino)pent-4-ynamido)-4-methylpentanoateYield 90.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of compound 2 (8.5 g; 31 mmol) in dry THF (100 mL) was added DIEA (16.02 g; 124 mmol) and the reaction mixture was stirred for 30 min at room temperature. Benzylchloroformate (6.87 g; 40.3 mmol) was added and stirring was continued at room temperature for 16 h. The solvent was removed on the rotary evaporator and the residue was taken up in ethyl acetate (150 mL) and washed sequentially with water (50 mL), 5% HCl (2×50 mL), and brine (50 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to give 3 as a white solid (10.46 g: 90% yield). 1H NMR (CDCl3) δ 7.3 (m, 5H), 6.7 (s, 1H), 5.6 (s, 1H), 5.1 (s, 2H), 4.6 (m, 1H), 4.4 (m, 1H), 3.7 (s, 3H), 2.6 (m, 2H), 2.8 (s, 1H), 2.6 (m, 1H), 1.6 (m, 2H), 1.5 (m, 1H), 0.9 (d, 6H).

Workup

  1. stirringstirring
  2. waitwas continued at room temperature for 16 h
  3. customThe solvent was removed on the rotary evaporator
  4. washwashed sequentially with water (50 mL), 5% HCl (2×50 mL), and brine (50 mL)
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-74690623dbbd45ab9e778fee6483639e
Source dataset
uspto-grants-2016_04
Patent number
US09309284B2

Reaction notes

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