Cesium carbonate → tert-butyl 4-(4-chloro-7-(phenylsulfonyl)-7H-pyrrolo[2,3-d]pyrimidin-6-yl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 871092Notes

Reaction equation

HRID 871092 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C(C)(C)OB([C:15]2[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17][CH:16]=2)O1.[Cl:29][C:30]1[C:31]2[CH:38]=[C:37](I)[N:36]([S:40]([C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)(=[O:42])=[O:41])[C:32]=2[N:33]=[CH:34][N:35]=1>O1CCCC1.O.C(OCC)(=O)C>[Cl:29][C:30]1[C:31]2[CH:38]=[C:37]([C:15]3[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:22])[CH2:17][CH:16]=3)[N:36]([S:40]([C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)(=[O:42])=[O:41])[C:32]=2[N:33]=[CH:34][N:35]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 574158854-Chloro-6-iodo-7-phenylsulfonyl-7H-pyrrolo[2,3-D]pyrimidine

Product 1

HCID 58709981tert-butyl 4-(4-chloro-7-(phenylsulfonyl)-7H-pyrrolo[2,3-d]pyrimidin-6-yl)-5,6-dihydropyridine-1(2H)-carboxylate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

A mixture of cesium carbonate (7.45 g, 22.88 mmol), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (0.778 g, 0.95 mmol), tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (3.98 g, 12.87 mmol), and 4-chloro-6-iodo-7-(phenylsulfonyl)-7H-pyrrolo[2,3-d]pyrimidine (5 g, 9.53 mmol) in tetrahydrofuran (50 mL) and water (8.33 mL) was heated at 65° C. for 16 hours, diluted with ethyl acetate and washed with water and brine. The organic layer was dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography on silica (IntelliFlash Varian 971-FP), eluting with a gradient of 5-80% ethyl acetate in heptanes to provide the title compound. ESI MS: 497.1 (M+Na)+.

Workup

  1. washwashed with water and brine
  2. dry with materialThe organic layer was dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by flash chromatography on silica (IntelliFlash Varian 971-FP)
  6. washeluting with a gradient of 5-80% ethyl acetate in heptanes

Sources & evidence

ORD record
ord-e5a01929a295416893fe28397bcf7091
Source dataset
uspto-grants-2015_03
Patent number
US08969375B2

Reaction notes

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