Pyrrolidine → 4-(3-Fluorobenzyloxy)-3-(2-(triisopropylsilyl)ethynyl)benzenamine

HRID 877107Notes

Reaction equation

Br[C:2]1[CH:16]=[C:15]([N+:17]([O-:19])=[O:18])[CH:14]=[CH:13][C:3]=1[O:4][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([F:12])[CH:7]=1.[C:20]([Si:22]([CH:29]([CH3:31])[CH3:30])([CH:26]([CH3:28])[CH3:27])[CH:23]([CH3:25])[CH3:24])#[CH:21].N1CCCC1>CN(C=O)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>[F:12][C:8]1[CH:7]=[C:6]([CH:11]=[CH:10][CH:9]=1)[CH2:5][O:4][C:3]1[CH:13]=[CH:14][C:15]([N+:17]([O-:19])=[O:18])=[CH:16][C:2]=1[C:21]#[C:20][Si:22]([CH:23]([CH3:25])[CH3:24])([CH:29]([CH3:31])[CH3:30])[CH:26]([CH3:28])[CH3:27].[F:12][C:8]1[CH:7]=[C:6]([CH:11]=[CH:10][CH:9]=1)[CH2:5][O:4][C:3]1[CH:13]=[CH:14][C:15]([NH2:17])=[CH:16][C:2]=1[C:21]#[C:20][Si:22]([CH:23]([CH3:25])[CH3:24])([CH:29]([CH3:31])[CH3:30])[CH:26]([CH3:28])[CH3:27]

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 1-((2-bromo-4-nitrophenoxy)methyl)-3-fluorobenzene (1 g), ethynyltriisopropylsilane (1.032 mL), pyrrolidine (0.3 mL) in DMF (20 mL) was added Pd(PPh3)2Cl2 (501 mg), CuI (117 mg) and the mixture was heated at 80° C. overnight. The solvent was removed, the residue was purified by flash chromatography, eluting with 10% EtOAc in hexane to give the desired product (2-(2-(3-fluorobenzyloxy)-5-nitrophenyl)ethynyl)triisopropylsilane (compound 23.1, 472 mg) and 4-(3-fluorobenzyloxy)-3-(2-(triisopropylsilyl)ethynyl)benzenamine (compound 23.2, 440 mg). LCMS ESI(+) m/z: 428 (M+1) and LCMS ESI(+) m/z: 398 (M+1).

Workup

customThe solvent was removed
customthe residue was purified by flash chromatography
washeluting with 10% EtOAc in hexane

Sources & evidence

ORD record: ord-bb93d7f4e3504348a5942ac9dd67077c
Source dataset: uspto-grants-2015_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08987284B2

Reaction notes

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