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

HRID 919646ノート

反応式

HRID 919646 の反応式
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

参加物

6

反応物 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

生成物 1

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

試薬・触媒・溶媒 1

HCID 31374Dimethylacetamide溶媒

反応条件

温度
115 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-16ce8639513c4a3298d40d611f1635a4
出典データセット
uspto-grants-2016_03
特許番号
US09273028B2

反応ノート

読み込み中…