Dichloromethane → 2-[(E)-2-(3,5-dimethoxyphenyl)vinyl]-5-(phenylsulfonyl)-5H-pyrrolo[2,3-b]pyrazine

HRID 1052242Notes

Reaction equation

HRID 1052242 reaction equation
Br[C:2]1[N:3]=[C:4]2[CH:10]=[CH:9][N:8]([S:11]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)(=[O:13])=[O:12])[C:5]2=[N:6][CH:7]=1.[CH3:20][O:21][C:22]1[CH:23]=[C:24](/[CH:30]=[CH:31]/B2OC(C)(C)C(C)(C)O2)[CH:25]=[C:26]([O:28][CH3:29])[CH:27]=1.ClCCl.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O>[CH3:29][O:28][C:26]1[CH:25]=[C:24](/[CH:30]=[CH:31]/[C:2]2[N:3]=[C:4]3[CH:10]=[CH:9][N:8]([S:11]([C:14]4[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=4)(=[O:13])=[O:12])[C:5]3=[N:6][CH:7]=2)[CH:23]=[C:22]([O:21][CH3:20])[CH:27]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 62657Potassium Phosphate, TribasicHCID 162181852-[(1E)-2-(3,5-Dimethoxyphenyl)ethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 899634192-Bromo-5-(phenylsulfonyl)-5H-pyrrolo[2,3-b]pyrazine

Product 1

HCID 899631882-[(E)-2-(3,5-dimethoxyphenyl)vinyl]-5-(phenylsulfonyl)-5H-pyrrolo[2,3-b]pyrazineYield 95%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
88 °C

Procedure

A stirred mixture of 2-bromo-5-(phenylsulfonyl)-5H-pyrrolo[2,3-b]pyrazine (929 mg, 2.75 mmol), 2-[(E)-2-(3,5-dimethoxyphenyl)vinyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (from Aldrich, cat#676160, 838 mg, 2.89 mmol), [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II), complex with dichloromethane (1:1) (140 mg, 0.171 mmol), and potassium phosphate (1.20 g, 5.65 mmol) in 1,4-dioxane (20 mL)/water (9.6 mL) was heated at 88° C. After 1 hour, the reaction mixture was quenched with saturated aq. NH4Cl and extracted with methylene chloride. The combined organic layers were dried over MgSO4, filtered, and then concentrated. The residue was purified on silica gel (eluting with 0 to 50% EtOAc in hexanes) to give the desired product (1.10 g, 95%). LCMS calculated for C22H20N3O4S (M+H)+: m/z=422.2. Found: 422.2.

Workup

  1. customthe reaction mixture was quenched with saturated aq. NH4Cl
  2. extractionextracted with methylene chloride
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified on silica gel (eluting with 0 to 50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-64b5732f4f374fa8a9f4ed4dcc5735e3
Source dataset
uspto-grants-2016_07
Patent number
US09388185B2

Reaction notes

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