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

HRID 595658
Notes
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Reaction equation

HRID 595658 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
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 903336636-chloro-2-(5-fluoro-1H-indol-2-yl)pyridin-3-yl trifluoromethanesulfonate

Product 1

HCID 903339502-(6-chloro-3-vinylpyridin-2-yl)-5-fluoro-1H-indoleYield 72.4%

Reagents, catalysts & solvents 2

HCID 178418476
HCID 178418476, compound
Catalyst
HCID 6228DimethylformamideSolvent

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

  1. additionwas added under N2 protection
  2. filtrationThen it was filtered
  3. concentrationconcentrated in vacuo
  4. 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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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes