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Tributylvinyltin → 2-(2-chloro-5-vinylpyrimidin-4-yl)-4-fluoro-1H-indole

HRID 595722
Notes
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Reaction equation

HRID 595722 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)=[C:20]([F:23])[CH:19]=[CH:18][CH:17]=3)=[N:9][C:10]([Cl:13])=[N: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)=[C:20]([F:23])[CH:19]=[CH:18][CH:17]=3)[C:7]([CH:26]=[CH2:27])=[CH:12][N:11]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 903410332-chloro-4-(4-fluoro-1H-indol-2-yl)pyrimidin-5-yl trifluoromethanesulfonate

Product 1

HCID 903334972-(2-chloro-5-vinylpyrimidin-4-yl)-4-fluoro-1H-indoleYield 72,494.703%

Reagents, catalysts & solvents 2

HCID 178418476
HCID 178418476, compound
Catalyst
HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a mixture of 2-chloro-4-(4-fluoro-1H-indol-2-yl)pyrimidin-5-yl trifluoromethanesulfonate (500 mg, 1.26 mmol), tributyl(vinyl)stannane (400 mg, 1.26 mmol) and anhydrous LiCl (150 mg, 3.54 mmol) in DMF (5 mL), Pd(PPh3)2Cl2 (50 mg, 0.07 mmol) was added under N2 protection. The reaction mixture was stirred at 60° C. for 1 h. Then it was concentrated in vacuo, and the residue was purified by column chromatography (PE:EA=10:1) to give the product of 2-(2-chloro-5-vinylpyrimidin-4-yl)-4-fluoro-1H-indole (250 g, yield: 72.3%). 1H-NMR (DMSO-d6, 400 MHz) δ 12.21 (br s, 1H), 8.85 (s, 1H), 7.41 (d, J=7.6 Hz, 1H), 7.21˜7.27 (m, 1H), 7.08˜7.20 (m, 2H), 6.87 (dd, J=10.4, 7.6 Hz, 1H), 6.01 (dd, J=17.6, 1.2 Hz, 1H), 5.72 (dd, J=11.2, 1.2 Hz, 1H). MS (M+H)+: 274/276.

Workup

  1. additionwas added under N2 protection
  2. concentrationThen it was concentrated in vacuo
  3. customthe residue was purified by column chromatography (PE:EA=10:1)

Sources & evidence

ORD record
ord-9f02695eb16946ae9d23e098efa43336
Source dataset
uspto-grants-2016_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09243002B2

Reaction notes

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