Cesium carbonate → tert-butyl 3-(6-((diphenylmethylene)amino)-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate

HRID 919646노트

반응식

HRID 919646 반응식
Br[C:2]1[N:7]=[CH:6][C:5]2[N:8]=[CH:9][N:10]([CH:11]3[CH2:16][CH2:15][CH2:14][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:12]3)[C:4]=2[CH:3]=1.[NH:24](C1C=CC=CC=1)C1C=CC=CC=1.C[C:38]1(C)[C:64]2[C:59](=[C:60](P(C3C=CC=CC=3)C3C=CC=CC=3)[CH:61]=[CH:62][CH:63]=2)O[C:40]2[C:41](P(C3C=CC=CC=3)C3C=CC=CC=3)=[CH:42][CH:43]=[CH:44][C:39]1=2.C([O-])([O-])=O.[Cs+].[Cs+]>CC(N(C)C)=O>[C:39]1([C:38](=[N:24][C:2]2[N:7]=[CH:6][C:5]3[N:8]=[CH:9][N:10]([CH:11]4[CH2:16][CH2:15][CH2:14][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:12]4)[C:4]=3[CH:3]=2)[C:64]2[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=2)[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1

참가 물질

6

반응물 4

HCID 10796Cesium carbonateHCID 11487DiphenylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 72344680tert-butyl 3-(6-bromo-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate

생성물 1

HCID 87946249tert-butyl 3-(6-((diphenylmethylene)amino)-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate수율 519.1%

시약·촉매·용매 1

HCID 31374Dimethylacetamide용매

반응 조건

온도
115 °C

실험 절차

To a solution of tert-butyl 3-(6-bromo-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate (0.6 g, 1.58 mmol, 1.0 eq) in DMA (5 mL) were added Ph2NH (430 mg, 2.37 mmol, 1.5 eq), Pd3(dba)2 (87 mg, 0.095 mmol, 0.06 eq), Xantphos (91 mg, 0.16 mmol, 0.1 eq) and Cs2CO3 (0.8 g, 2.5 mmol, 1.6 eq) at rt under N2. The mixture was stirred at 115° C. for 16 h, cooled to rt and the solid was filtered off and washed with EtOAc (30 mL). The organic layer was washed with H2O (20 mL×2) and brine (10 mL), separated, dried (Na2SO4) and concentration in vacuo to afford a residue which was purified by silica gel column chromatography with EtOAc in PE (1/1 v/v) to give the title compound (0.4 g, 50%) as brown solid. 1H NMR (400 MHz, CDCl3) δ: 8.80 (s, 1H), 7.89 (s, 1H), 7.82 (d, 2H), 7.52-7.48 (m, 1H), 7.44-7.40 (m, 2H), 7.27-7.24 (m, 3H), 7.24-7.17 (m, 2H), 6.68 (s, 1H), 4.13-4.09 (m, 2H), 3.95-3.92 (m, 1H), 3.18-3.14 (m, 1H), 3.01-2.94 (m, 1H), 1.95-1.90 (m, 2H), 1.79-1.76 (m, 1H), 1.63-1.60 (m, 1H), 1.53 (s, 9H). ESI-MS (M+H+): 382.0.

후처리

  1. temperaturecooled to rt
  2. filtrationthe solid was filtered off
  3. washwashed with EtOAc (30 mL)
  4. washThe organic layer was washed with H2O (20 mL×2) and brine (10 mL)
  5. customseparated
  6. customdried
  7. concentration(Na2SO4) and concentration in vacuo
  8. customto afford a residue which
  9. customwas purified by silica gel column chromatography with EtOAc in PE (1/1 v/v)

출처 및 근거

ORD 기록
ord-16ce8639513c4a3298d40d611f1635a4
출처 데이터셋
uspto-grants-2016_03
특허 번호
US09273028B2

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