Sodium Carbonate → N,N-dimethyl-3-(3-methyl-1-(1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine-2-yl)but-1-enyl)benzenamine

HRID 1515950Notes

Reaction equation

HRID 1515950 reaction equation
[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[CH:17][CH:18]=[C:13]3[CH:12]=[C:11]2[C:19](OS(C2C=CC(C)=CC=2)(=O)=O)=[CH:20][CH:21]([CH3:23])[CH3:22])(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:35][N:36]([CH3:46])[C:37]1[CH:38]=[C:39](B(O)O)[CH:40]=[CH:41][CH:42]=1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.C(OCC)(=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>[CH3:35][N:36]([CH3:46])[C:37]1[CH:38]=[CH:39][CH:40]=[C:41]([C:19]([C:11]2[N:10]([S:7]([C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)(=[O:9])=[O:8])[C:14]3=[N:15][CH:16]=[CH:17][CH:18]=[C:13]3[CH:12]=2)=[CH:20][CH:21]([CH3:23])[CH3:22])[CH:42]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27625273-(Dimethylamino)benzeneboronic acidHCID 86654521toluene-4-sulfonic acid-1-(1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-2-yl)-3-methyl-but-1-enyl ester

Product 1

HCID 67229151N,N-dimethyl-3-(3-methyl-1-(1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine-2-yl)but-1-enyl)benzenamineYield 84.2%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
25 °C

Procedure

A suspension of toluene-4-sulfonic acid-1-(1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-2-yl)-3-methyl-but-1-enyl ester (prepared as in Example 130, 4.0 g, 8.0 mmol), 3-(dimethylamino)phenylboronic acid (3.3 g, 20 mmol), bis(triphenylphosphine)palladium(II) dichloride (567 mg, 0.8 mmol) in 1,4-dioxane (40 mL) and an aqueous sodium carbonate solution (2N, 21 mL) was heated in a microwave reactor to 100° C. for 3 h under nitrogen. At this time, the reaction was cooled to 25° C., diluted with ethyl acetate (50 mL) and then washed with a saturated aqueous sodium bicarbonate solution (2×50 mL). The organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Silica gel column chromatography (60 g, petroleum ether/ethyl acetate 15:1) afforded N,N-dimethyl-3-(3-methyl-1-(1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine-2-yl)but-1-enyl)benzenamine (3.0 g, 83%) as a yellow solid: 1H NMR (300 MHz, CDCl3) δ ppm 8.48 (dd, 1H, J1=4.5 Hz, J2=3.6 Hz), 7.85 (dd, 1H, J1=7.8 Hz, J2=1.2 Hz), 7.65 (d, 2H, J=7.8 Hz), 7.38-7.36 (m, 1H), 7.31-7.14 (m, 4H), 7.06 (t, 1H, J=8.1 Hz), 6.65-6.48 (m, 3H), 6.14 (d, 1H, J=10.2 Hz), 2.77 (s, 6H), 2.72-2.64 (m, 1H), 1.14 (s, 3H), 1.12 (s, 3H).

Workup

  1. washwashed with a saturated aqueous sodium bicarbonate solution (2×50 mL)
  2. dry with materialThe organic layers were dried over anhydrous sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6e5715fcf6204e6bbf14a5e5a5fb1617
Source dataset
uspto-grants-2012_07
Patent number
US08222416B2

Reaction notes

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