Propyne → HCID 69340020, compound

HRID 1241481Notes

Reaction equation

HRID 1241481 reaction equation
[CH:1]#[C:2][CH3:3].[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([C@@H:11]2[N:17]([C@@H:18]([C:20]3[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][CH:21]=3)[CH3:19])[C:16](=[O:27])[C:15]3[CH:28]=[C:29](I)[CH:30]=[CH:31][C:14]=3[NH:13][C:12]2=[O:33])=[CH:7][CH:6]=1.C(N(CC)CC)C>[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(#N)C>[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([C@@H:11]2[N:17]([C@@H:18]([C:20]3[CH:25]=[CH:24][C:23]([Cl:26])=[CH:22][CH:21]=3)[CH3:19])[C:16](=[O:27])[C:15]3[CH:28]=[C:29]([C:1]#[C:2][CH3:3])[CH:30]=[CH:31][C:14]=3[NH:13][C:12]2=[O:33])=[CH:7][CH:6]=1

Participants

7

Reactant 3

HCID 6335PropyneHCID 8471TriethylamineHCID 69340572HCID 69340572, compound

Product 1

HCID 69340020HCID 69340020, compoundYield 89%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

Propyne (2 mL) was condensed in a sealed tube at −78° C. Then, (3S)-3-(4-Chlorophenyl)-4-[(R)-1-(4-chlorophenyl)ethyl]-7-iodo-1,4-benzodiazepine-2,5-dione (200 mg, 0.362 mmol), copper iodide (15 mg, 0.0788 mmol), dichlorobis(triphenylphosphine)palladium (II) (39 mg, 0.0556 mmol), triethylamine (2 mL), and acetonitrile (4 mL) were added. The sealed tube was closed and the reaction mixture was allowed warm up to room temperature. After 12 h, the reaction mixture was cooled to −78° C. and the sealed tube was opened and allowed to warm up to room temperature under vigorous stirring. Then, solvents were evaporated in vacuo and the residue was purified by column chromatgraphy on silica (EtOAc/Hexanes, 1:1) to give the title compound as colorless solid (150 mg, 89%): 1H NMR (400 MHz, CDCl3) δ 1.73 (d, J=7.1 Hz, 3H), 2.06 (s, 3H), 5.24 (s, 1H), 6.49 (q, J=7.1 Hz, 1H), 6.62–6.65 (m, 3H), 6.93 (d, J=8.4 Hz, 2H), 7.20 (dd, J=8.0 Hz, J=2.0 Hz, 1H), 7.33 (d, J=8.4 Hz, 2H), 7.53 (d, J=8.8 Hz, 2H), 7.79 (d, J=2.0 Hz, 1H), 8.57 (br s, 1H). Mass spectrum (LCMS, ESI pos.): Calcd for C26H20Cl2N2O2: 463; found: 464 (M+H)+.

Workup

  1. customcondensed in a sealed tube at −78° C
  2. customThe sealed tube was closed
  3. temperaturethe reaction mixture was cooled to −78° C.
  4. temperatureto warm up to room temperature under vigorous stirring
  5. customThen, solvents were evaporated in vacuo
  6. customthe residue was purified by column chromatgraphy on silica (EtOAc/Hexanes, 1:1)

Sources & evidence

ORD record
ord-0fa38c58587e45fe91f0e9c1ef5ff433
Source dataset
uspto-grants-2006_10
Patent number
US07115598B2

Reaction notes

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