Propyne → HCID 59860342, compound

HRID 252113Notes

Reaction equation

HRID 252113 reaction equation
Cl.[Cl:2][C:3]1[CH:22]=[C:21]([Cl:23])[CH:20]=[CH:19][C:4]=1[CH2:5][NH:6][CH:7]1[CH2:11][CH2:10][N:9]([C:12]2[CH:17]=[CH:16][C:15](I)=[CH:14][N:13]=2)[CH2:8]1.[CH:24]#[C:25][CH3:26]>ClCCl.C(N(CC)CC)C.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.[Cu]I>[Cl:2][C:3]1[CH:22]=[C:21]([Cl:23])[CH:20]=[CH:19][C:4]=1[CH2:5][NH:6][C@H:7]1[CH2:11][CH2:10][N:9]([C:12]2[CH:17]=[CH:16][C:15]([C:24]#[C:25][CH3:26])=[CH:14][N:13]=2)[CH2:8]1

Participants

7

Reactant 2

HCID 6335PropyneHCID 66854200HCID 66854200, compound

Product 1

HCID 59860342HCID 59860342, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

Dissolve (2,4-dichlorobenzyl)-[1-(5-iodopyridin-2-yl)-pyrrolidin-3-yl]-amine hydrochloride (130 mg, 0.27 mmol) in dichloromethane (10 mL) and triethylamine (10 mL). Add trans-dichlorobis(triphenylphosphine)palladium (II) (10 mg, 0.014 mmol) and copper(I) iodide (3 mg, 0.016 mmol). Bubble propyne into the mixture for 1 min. Stir the mixture overnight, filter it through a pad of Celite®, concentrate and chromatograph on silica gel, eluting with 10:90 to 1:1 ethyl acetate:hexanes, to give the title compound as a residue. Dissolve the residue in methanol, add 1 N HCl in methanol (1 mL). Concentrate and dry in vacuum oven at 60° C. to give the title compound as its hydrochloride salt as a light yellow solid (95 mg, 89%). δ 1H NMR (400 MHz, MeOH-d4) δ 8.03 (d, 1H, J=1.6 Hz), 7.84 (d, 1H, J=8.8 Hz), 7.69-7.68 (m, 2H), 7.49 (dd, 1H, J=8.0, 2.2 Hz), 6.95 (d, 1H, J=9.6 Hz), 4.53-4.45 (m, 2H), 4.28-4.23 (m, 1H), 4.10-4.06 (m, 1H), 3.90-3.83 (m, 2H), 3.72-3.66 (m, 1H), 2.73-2.65 (m, 1H), 2.50-2.41 (m, 1H), 2.03 (s, 3H), MS (ES): m/z=360 [M+H].

Workup

  1. filtrationfilter it through a pad of Celite®
  2. concentrationconcentrate
  3. washchromatograph on silica gel, eluting with 10:90 to 1:1 ethyl acetate

Sources & evidence

ORD record
ord-4ab472b5781e477cbdd0def8144fa950
Source dataset
uspto-grants-2011_01
Patent number
US07868014B2

Reaction notes

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