Potassium Phosphate, Tribasic → 3-(1-phenylsulfonyl-4-hex-1-enyl-1H-pyrazol-3-yl)-pyridine

HRID 1027539Notes

Reaction equation

HRID 1027539 reaction equation
[C:1]1([S:7]([N:10]2[CH:14]=[C:13](Br)[C:12]([C:16]3[CH:17]=[N:18][CH:19]=[CH:20][CH:21]=3)=[N:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH:22](/B(O)O)=[CH:23]\[CH2:24][CH2:25][CH2:26][CH3:27].[O-]P([O-])([O-])=O.[K+].[K+].[K+].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C=CC=CC=1>[C:1]1([S:7]([N:10]2[CH:14]=[C:13]([CH:22]=[CH:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:12]([C:16]3[CH:17]=[N:18][CH:19]=[CH:20][CH:21]=3)=[N:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 5326225B-(1E)-1-Hexenylboronic acidHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 575480773-(1-Phenylsulfonyl-4-bromo-1H-pyrazol-3-yl)-pyridine

Product 1

HCID 672844273-(1-phenylsulfonyl-4-hex-1-enyl-1H-pyrazol-3-yl)-pyridineYield 61%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To toluene (20 ml) containing 36A (0.67 g, 1.84 mmol) (see Scheme 7), was added 1.5 eq of (E)-hexene-1-ylboronic acid (0.35 g). The resulting mixture was stirred for 2 hours under N2. Successively were added 2 eq of K3PO4 (0.78 g), 4 mol % of Pd(OAc)2 (16.5 mg) and 8 mol % of S-Phos (60.4 mg). After the addition, the resulting solution was warmed at 90° C. for 18 hours under N2. After cooling to room temperature, the mixture was diluted with ethyl acetate, washed three times with a saturated NaHCO3 solution, dried (Na2SO4), filtered and concentrated. The resulting residue was purified by flash chromatography (diethyl ether/PE 1/1) to afford 3-(1-phenylsulfonyl-4-hex-1-enyl-1H-pyrazol-3-yl)-pyridine (46A) as an oil (0.38 g, 61%). 1H-NMR (400 MHz, CDCl3): δ 8.8 (d, J=2 Hz, 1H), 8.6 (dd, J=5 Hz, 2 Hz, 1H), 8.15 (s, 1H), 8.10-8.05 (m, 2H), 7.94 (dt, J=8 Hz, 2 Hz, 1H), 7.70-7.64 (m, 1H), 7.56 (bt, J=8 Hz, 2H), 7.37-7.33 (m, 1H), 6.19-6.02 (m, 1H), 2.2-2.13 (m, 2H), 1.45-1.29 (m, 4H), 0.90 (t, J=7 Hz, 3H).

Workup

  1. additionAfter the addition
  2. temperatureAfter cooling to room temperature
  3. washwashed three times with a saturated NaHCO3 solution
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe resulting residue was purified by flash chromatography (diethyl ether/PE 1/1)

Sources & evidence

ORD record
ord-0f455873e74b45acae06d6ed65c97f0d
Source dataset
uspto-grants-2014_05
Patent number
US08735388B2

Reaction notes

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