Water → 1-(Tert-butoxycarbonyl)-2-[2-(4-ethoxycarbonylphenyl)ethynyl]pyrrolidine

HRID 350337

Reaction equation

HRID 350337 reaction equation
I[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.[C:13]([O:17][C:18]([N:20]1[CH2:24][CH2:23][CH2:22][CH:21]1[C:25]#[CH:26])=[O:19])([CH3:16])([CH3:15])[CH3:14].O>N(C(C)C)C(C)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:13]([O:17][C:18]([N:20]1[CH2:24][CH2:23][CH2:22][CH:21]1[C:25]#[C:26][C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1)=[O:19])([CH3:16])([CH3:15])[CH3:14]

Participants

7

Reactant 3

HCID 962WaterHCID 142891Ethyl 4-iodobenzoateHCID 14730283tert-Butyl 2-ethynylpyrrolidine-1-carboxylate

Product 1

HCID 235119181-(Tert-butoxycarbonyl)-2-[2-(4-ethoxycarbonylphenyl)ethynyl]pyrrolidineYield 81%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 7912DiisopropylamineSolvent2×

Procedure

A suspension of ethyl 4-iodobenzoate (1.7 mL, 10 mmol), Pd(PPh3)4 (578 mg, 0.5 mmol), and CuI (190 mmol, 1 mmol) in i-Pr2NH (20 mL) was stirred for 0.5 hr under N2. To this mixture was added a solution of 1-(tert-butoxycarbonyl)-2-ethynylpyrrolidine (1.95 g, 10 mmol) in i-Pr2NH (20 mL) for over 10 min. After stirring for 3 hr at room temp, the mixture was poured into H2O and extracted with EtOAc. The extract was washed with brine, dried over MgSO4, and evaporated. The residue was chromatographed on silica-gel with n-hexane-AcOEt (10:1, v/v) as eluent to give 2.77 g (81%) 1-(tert-butyloxycarbonyl)-2-(2-(4-ethoxycarbonylphenyl)ethynyl) pyrrolidine as a colorless oil. 1H-NMR (CDCl3) δ 1.37 (3 H, t, J=6.8 Hz), 1.49 (9 H, s), 1.85–2.12 (4 H, m), 3.37–3.51 (2 H, m), 4.37 (2 H, q, J=6.8 Hz), 4.54–4.77 (1 H, m), 7.44 (2 H, d, J=7.8 Hz), 7.96 (2 H, d, J=7.8 Hz)

Workup

  1. stirringAfter stirring for 3 hr at room temp
  2. extractionextracted with EtOAc
  3. washThe extract was washed with brine
  4. dry with materialdried over MgSO4
  5. customevaporated
  6. customThe residue was chromatographed on silica-gel with n-hexane-AcOEt (10:1

Sources & evidence

ORD record
ord-8c91533897ca4fedaf41f96cd39e04ce
Source dataset
uspto-grants-2007_02
Patent number
US07179819B2

Linked notes

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