Tributylvinyltin → 2-(6-chloro-3-vinylpyridin-2-yl)-5-fluoro-1H-indole

HRID 595658Notes

Reaction equation

FC(F)(F)S(O[C:7]1[C:8]([C:14]2[NH:15][C:16]3[C:21]([CH:22]=2)=[CH:20][C:19]([F:23])=[CH:18][CH:17]=3)=[N:9][C:10]([Cl:13])=[CH:11][CH:12]=1)(=O)=O.[CH2:26]([Sn](CCCC)(CCCC)C=C)[CH2:27]CC.[Li+].[Cl-]>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>[Cl:13][C:10]1[N:9]=[C:8]([C:14]2[NH:15][C:16]3[C:21]([CH:22]=2)=[CH:20][C:19]([F:23])=[CH:18][CH:17]=3)[C:7]([CH:26]=[CH2:27])=[CH:12][CH:11]=1

Participants

Conditions

Temperature: 50 °C

Procedure

To a mixture of 6-chloro-2-(5-fluoro-1H-indol-2-yl)pyridin-3-yl trifluoromethanesulfonate (200 mg, 0.51 mmol), tributyl(vinyl)stannane (170 mg, 0.54 mmol) and anhydrous LiCl (70 mg, 1.65 mmol) in DMF (2 mL), Pd(PPh3)2Cl2 (30 mg, 0.04 mmol) was added under N2 protection. The reaction mixture was stirred at 50° C. for 1 h. Then it was filtered and concentrated in vacuo, the residue was purified by column chromatography (PE: EA=20:1) to give the product of 2-(6-chloro-3-vinylpyridin-2-yl)-5-fluoro-1H-indole (100 mg, yield: 72.4%). 1H-NMR (CDCl3, 400 MHz) δ 11.67 (br s, 1H), 8.05 (d, J=8.4 Hz, 1H), 7.45˜7.55 (m, 2H), 7.38 (d, J=10.0 Hz, 1H), 7.15 (dd, J=17.2, 11.2 Hz, 1H), 7.00˜7.06 (m, 1H), 6.84 (d, J=2.0 Hz, 1H), 5.93 (d, J=17.2 Hz, 1H), 5.59 (d, J=11.2 Hz, 1H). MS (M+H)+: 273/275.

Workup

additionwas added under N2 protection
filtrationThen it was filtered
concentrationconcentrated in vacuo
customthe residue was purified by column chromatography (PE: EA=20:1)

Sources & evidence

ORD record: ord-8357e0d21e204094b074150830f926db
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09243002B2

Reaction notes

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