Water → Carbamic acid, [4-[1-[(4-methylphenyl)sulfonyl]-1H-pyrrolo[2,3-b]pyridin-3-yl]-2-thienyl]-, 1,1-dimethylethyl ester (9CI)

HRID 2108747Notes

Reaction equation

HRID 2108747 reaction equation
CC1(C)C(C)(C)OB([C:9]2[C:17]3[C:12](=[N:13][CH:14]=[CH:15][CH:16]=3)[N:11]([S:18]([C:21]3[CH:27]=[CH:26][C:24]([CH3:25])=[CH:23][CH:22]=3)(=[O:20])=[O:19])[CH:10]=2)O1.Br[C:30]1[CH:31]=[C:32]([NH:35][C:36](=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39])[S:33][CH:34]=1.C(=O)([O-])[O-].[K+].[K+].O>COCCOC.CCOC(C)=O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[S:18]([N:11]1[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:17]2[C:9]([C:30]2[CH:31]=[C:32]([NH:35][C:36](=[O:42])[O:37][C:38]([CH3:40])([CH3:39])[CH3:41])[S:33][CH:34]=2)=[CH:10]1)([C:21]1[CH:27]=[CH:26][C:24]([CH3:25])=[CH:23][CH:22]=1)(=[O:20])=[O:19]

Participants

8

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 497589593-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1-tosyl-1H-pyrrolo[2,3-b]pyridineHCID 56763855tert-Butyl (4-bromothiophen-2-yl)carbamate

Product 1

HCID 57633069Carbamic acid, [4-[1-[(4-methylphenyl)sulfonyl]-1H-pyrrolo[2,3-b]pyridin-3-yl]-2-thienyl]-, 1,1-dimethylethyl ester (9CI)Yield 38%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-tosyl-1H-pyrrolo[2,3-b]pyridine (398 mg, 1 mmol), tert-butyl 4-bromothiophen-2-ylcarbamate (190 mg, 0.68 mmol), potassium carbonate (310 mg, 2.25 mmol), and tetrakis(triphenylphosphine) palladium (0) (20 mg) were combined in 4 mL DME, 1 mL water, and heated to 160° C. in the microwave for 10 minutes, followed by 170° C. for 10 minutes. The reaction mixture was diluted with EtOAc and washed with saturated sodium bicarbonate. The organic layer was filtered through celite and concentrated to an oil which was purified by column chromatography on silica (15 to 60% EtOAc/hexanes) to give the product as a brown foam, 0.12 g, 0.26 mmol, 38% yield. MH+ 470.1.

Workup

  1. washwashed with saturated sodium bicarbonate
  2. filtrationThe organic layer was filtered through celite
  3. concentrationconcentrated to an oil which
  4. customwas purified by column chromatography on silica (15 to 60% EtOAc/hexanes)

Sources & evidence

ORD record
ord-c4759cfd080a4d46afb88938193b4649
Source dataset
uspto-grants-2009_04
Patent number
US07514448B2

Reaction notes

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