Triphenylphosphine → tert-butyl-3-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyrrolidine-1-carboxylate

HRID 928199Notes

Reaction equation

HRID 928199 reaction equation
[CH3:1][C:2]1[C:6]([N+:7]([O-:9])=[O:8])=[CH:5][NH:4][N:3]=1.[C:10]([O:14][C:15]([N:17]1[CH2:21][CH2:20][CH:19](O)[CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[C:10]([O:14][C:15]([N:17]1[CH2:21][CH2:20][CH:19]([N:4]2[CH:5]=[C:6]([N+:7]([O-:9])=[O:8])[C:2]([CH3:1])=[N:3]2)[CH2:18]1)=[O:16])([CH3:13])([CH3:11])[CH3:12]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 44169391-Boc-3-pyrrolidinolHCID 178434564HCID 178434564, compound

Product 1

HCID 69092482tert-butyl-3-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyrrolidine-1-carboxylateYield 35.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 3-methyl-4-nitro-1H-pyrazole (3.0 g, 23.6 mmol, 1.00 eq), tert-butyl-3-hydroxypyrrolidine-1-carboxylate (4.42 g, 23.6 mmol, 1.00 eq), and triphenylphosphine (6.19 g, 23.6 mmol, 1.00 eq) in THF (60 mL) was added a solution of diethyl azodicarboxylate (4.34 mL, 23.6 mmol, 1.00 eq) in THF (10 mL) in a drop-wise manner over 30 min. The reaction mixture was allowed to stir at ambient temperature for 20 hr and then concentrated. The crude reaction mixture was purified via repeated flash chromatography on silica gel eluting with a gradient of 0-35% EtOAc in heptane to give the title compound (2.48 g, 35% yield) as a colorless oil that was the early eluting of two structural isomers. 1H NMR (400 MHz, CDCl3) δ ppm 8.15 (s, 1 H) 4.80 (quin, J=5.7 Hz, 1 H) 3.83 (dd, J=6.0, 12.0 Hz, 1 H) 3.79-3.45 (m, 3 H) 2.52 (s, 3 H) 2.38 (q, J=7.0 Hz, 2 H) 1.46 (s, 9 H). m/z (APCI+) for C13H21N4O4 197.2 (M+H)+.

Workup

  1. concentrationconcentrated
  2. customThe crude reaction mixture
  3. customwas purified

Sources & evidence

ORD record
ord-133731aeda354787b31bb7314cbd0ffe
Source dataset
uspto-grants-2016_03
Patent number
US09290496B2

Reaction notes

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