Potassium Carbonate → HCID 68579599, compound

HRID 641629Notes

Reaction equation

HRID 641629 reaction equation
Br[C:2]1[S:14][C:13]2[C:12]3[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=3[CH:6]([CH2:15][CH3:16])[N:5]([S:17]([C:20]3[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=3)(=[O:19])=[O:18])[C:4]=2[CH:3]=1.[S:28]1[CH:32]=[CH:31][C:30](B(O)O)=[CH:29]1.C(=O)([O-])[O-].[K+].[K+]>C(COC)OC.C(Cl)Cl.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:15]([CH:6]1[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:12]=2[C:13]2[S:14][C:2]([C:30]3[CH:31]=[CH:32][S:28][CH:29]=3)=[CH:3][C:4]=2[N:5]1[S:17]([C:20]1[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=1)(=[O:18])=[O:19])[CH3:16]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 581760Thiophene-3-boronic acidHCID 58669396HCID 58669396, compound

Product 1

HCID 68579599HCID 68579599, compoundYield 71%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6344DichloromethaneSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
75 °C

Procedure

2-Bromo-5-ethyl-4-[(4-methoxyphenyl)sulfonyl]-4,5-dihydrothieno[3,2-c]isoquinoline (1.02 g, 2.2 mmol), 3-thiopheneboronic acid (0.37 g, 2.9 mol), potassium carbonate (0.91 g, 6.6 mol) and [1.1′-bis(diphenylphosphino)ferrocene]dichloropalladium [II] (90 mg, 0.11 mmol) were combined in 40% aqueous dimethoxyethane (11 mL) and the mixture was heated to 75° C. After 3.5 h the mixture was cooled to 23° C., filtered through Celite and washed with ethyl acetate (125 mL). The filtrate was washed with 1 N aqueous sodium hydroxide and brine (125 mL each), dried (K2CO3), and concentrated in vacuo to give the crude product (0.91 g) as a tan solid which was taken up in methylene chloride (ca. 3 mL) and pre-adsorbed on silica gel (3 g). Flash chromatography on silica gel (27 g) eluting 25-, and then 50% methylene chloride-hexane gave the title compound (0.73 g, 71%, m.p. 182-84° C.) as a white solid which was pure enough for further use.

Workup

  1. temperatureAfter 3.5 h the mixture was cooled to 23° C.
  2. filtrationfiltered through Celite
  3. washwashed with ethyl acetate (125 mL)
  4. washThe filtrate was washed with 1 N aqueous sodium hydroxide and brine (125 mL each)
  5. dry with materialdried (K2CO3)
  6. concentrationconcentrated in vacuo
  7. customto give the crude product (0.91 g) as a tan solid which
  8. washFlash chromatography on silica gel (27 g) eluting 25-

Sources & evidence

ORD record
ord-d22f367dc2d0478abedc954f49599525
Source dataset
uspto-grants-2010_04
Patent number
US07696221B2

Reaction notes

Loading…