Cesium carbonate → HCID 67517143, compound

HRID 919639Notes

Reaction equation

HRID 919639 reaction equation
Cl[C:2]1[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][N:5]=[C:4]2[N:12]([S:15]([C:18]3[CH:24]=[CH:23][C:21]([CH3:22])=[CH:20][CH:19]=3)(=[O:17])=[O:16])[CH:13]=[CH:14][C:3]=12.[NH2:25][CH:26]1[CH2:31][CH2:30][CH2:29][N:28]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[CH2:27]1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:35]([O:34][C:32]([N:28]1[CH2:29][CH2:30][CH2:31][CH:26]([NH:25][C:2]2[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][N:5]=[C:4]3[N:12]([S:15]([C:18]4[CH:24]=[CH:23][C:21]([CH3:22])=[CH:20][CH:19]=4)(=[O:17])=[O:16])[CH:13]=[CH:14][C:3]=23)[CH2:27]1)=[O:33])([CH3:38])([CH3:36])[CH3:37]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 5458091-BOC-3-AminopiperidineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 67517666HCID 67517666, compound

Product 1

HCID 67517143HCID 67517143, compoundYield 46.7%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

To a solution of methyl 4-chloro-1-tosyl-1H-pyrrolo[2,3-b]pyridine-5-carboxylate (1 g, 2.7 mmol, 1.0 eq) and tert-butyl 3-aminopiperidine-1-carboxylate (659 mg, 3.3 mmol, 1.2 eq) in PhCH3 (20 mL) was added Pd(OAc)2 (65 mg, 0.27 mmol, 0.1 eq), xantphos (250 mg, 0.41 mmol, 0.15 eq) and. Cs2CO3 (2.64 g, 8.1 mmol, 3.0 eq) and the mixture was heated at 100° C. for 16 h. After cooling to rt, the mixture was filtered and the filtrate was concentrated in vacuo to afford an oil which was purified by silica gel column chromatography (PE/EA=8:1) to give the title compound as white solid (667 mg, yield: 46%). 1H NMR (400 MHz, CDCl3) δ: 8.91 (d, 1H), 8.72 (s, 1H), 7.96 (d, 2H), 7.45 (d, 1H), 7.18 (d, 2H), 3.77 (s, 3H), 3.67-3.57 (m, 1H), 3.13-2.97 (m, 2H), 2.29 (s, 3H), 1.98-1.96 (m, 2H), 1.83-1.67 (m, 2H), 1.64-1.46 (m, 3H), 1.40-1.25 (m, 9H). ESI-MS (M+H)+: 529.20.

Workup

  1. filtrationthe mixture was filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. customto afford an oil which
  4. customwas purified by silica gel column chromatography (PE/EA=8:1)

Sources & evidence

ORD record
ord-85c3a37fb9244b0a8c4a5d2153bbe3ed
Source dataset
uspto-grants-2016_03
Patent number
US09273028B2

Reaction notes

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