Triphenylphosphine → 4-methoxybenzyl N-[4-bromo-1-(tert-butoxycarbonyl)-1H-pyrazol-3-yl]-N-[(2,2,2-trichloroethoxy)carbonyl]leucinate

HRID 1744130

Reaction equation

HRID 1744130 reaction equation
[Br:1][C:2]1[C:3]([NH:14][C:15]([O:17][CH2:18][C:19]([Cl:22])([Cl:21])[Cl:20])=[O:16])=[N:4][N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH:6]=1.O[CH:24]([CH2:37][CH:38]([CH3:40])[CH3:39])[C:25]([O:27][CH2:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=1)=[O:26].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>CN(C=O)C.O>[Br:1][C:2]1[C:3]([N:14]([C:15]([O:17][CH2:18][C:19]([Cl:20])([Cl:22])[Cl:21])=[O:16])[C@H:24]([C:25]([O:27][CH2:28][C:29]2[CH:30]=[CH:31][C:32]([O:35][CH3:36])=[CH:33][CH:34]=2)=[O:26])[CH2:37][CH:38]([CH3:40])[CH3:39])=[N:4][N:5]([C:7]([O:9][C:10]([CH3:12])([CH3:13])[CH3:11])=[O:8])[CH:6]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 22235916HCID 22235916, compoundHCID 222360714-Methoxybenzyl 2-hydroxy-4-methylpentanoate

Product 1

HCID 691522654-methoxybenzyl N-[4-bromo-1-(tert-butoxycarbonyl)-1H-pyrazol-3-yl]-N-[(2,2,2-trichloroethoxy)carbonyl]leucinate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To tert-butyl 4-bromo-3-{[(2,2,2-trichloroethoxy)carbonyl]amino}-1H-pyrazole-1-carboxylate (2.32 g, 5.3 mmol), 4-methoxybenzyl 2-hydroxy-4-methylpentanoate (2.02 g, 8.0 mmol, prepared as described in Example 16) and triphenyl phosphine (2.1 g, 8.0 mmol) in dry DMF (50 mL) at 0° C. under dry nitrogen was added diisopropyl azodicarboxylate (1.6 mL, 8.0 mmol) dropwise and the reaction was stirred overnight. The reaction was poured into water and the product extracted with Et2O (2×), dried over Na2SO4, concentrated in vacuo and purified by flash chromatography over silica gel (EtOAc/Hex, 2/8) to afford 4-methoxybenzyl N-[4-bromo-1-(tert-butoxycarbonyl)-1H-pyrazol-3-yl]—N-[(2,2,2-trichloroethoxy)carbonyl]leucinate.

Workup

  1. extractionthe product extracted with Et2O (2×)
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. custompurified by flash chromatography over silica gel (EtOAc/Hex, 2/8)

Sources & evidence

ORD record
ord-701385ae05034063819110b4904b4ec0
Source dataset
uspto-grants-2006_03
Patent number
US07012075B2

Linked notes

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