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Potassium Acetate → 1,1-dimethylethyl 7-(2-methyl-1-{[(2-methylpropyl)-oxy]carbonyl}-1H-imidazo[4,5-b]pyridine-6-yl)-2,3-dihydro-1,4-benzoxazepine-4(5H)carboxylate

HRID 241148
ノート
印刷プレビュー

反応式

HRID 241148 の反応式
Br[C:2]1[CH:3]=[C:4]2[N:10]([C:11]([O:13][CH2:14][CH:15]([CH3:17])[CH3:16])=[O:12])[C:9]([CH3:18])=[N:8][C:5]2=[N:6][CH:7]=1.[CH3:19][C:20]([O:23][C:24]([N:26]1[CH2:32][C:31]2[CH:33]=[C:34](B(O)O)[CH:35]=[CH:36][C:30]=2[O:29][CH2:28][CH2:27]1)=[O:25])([CH3:22])[CH3:21].C([O-])(=O)C.[K+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:18][C:9]1[N:10]([C:11]([O:13][CH2:14][CH:15]([CH3:17])[CH3:16])=[O:12])[C:4]2[C:5]([N:8]=1)=[N:6][CH:7]=[C:2]([C:34]1[CH:35]=[CH:36][C:30]3[O:29][CH2:28][CH2:27][N:26]([C:24]([O:23][C:20]([CH3:21])([CH3:19])[CH3:22])=[O:25])[CH2:32][C:31]=3[CH:33]=1)[CH:3]=2
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

HCID 517044Potassium AcetateHCID 59604707(4-(Tert-butoxycarbonyl)-2,3,4,5-tetrahydrobenzo[f][1,4]oxazepin-7-yl)boronic acidHCID 66820076isobutyl 6-bromo-2-methyl-1H-imidazo[4,5-b]pyridine-1-carboxylate

生成物 1

HCID 668201401,1-dimethylethyl 7-(2-methyl-1-{[(2-methylpropyl)-oxy]carbonyl}-1H-imidazo[4,5-b]pyridine-6-yl)-2,3-dihydro-1,4-benzoxazepine-4(5H)carboxylate収率 33%

試薬・触媒・溶媒 2

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒
HCID 312751,4-Dioxane溶媒

反応条件

温度
95 °C

実験手順

A mixture of isobutyl 6-bromo-2-methyl-1H-imidazo[4,5-b]pyridine-1-carboxylate (2.2 g, 7.1 mmol) (reagent preparation 19), (4-{[(1,1-dimethylethyl)oxy]carbonyl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)boronic acid (2.7 g, 9.2 mmol, example 1, step 2), potassium acetate (2.8 g, 28.3 mmol), and dichloro[1,1-bis(diphenylphosphino]-ferrocenepalladium (II) dichloromethane adduct (0.78 g, 1.1 mmol) in dioxane (50 ml) was stirred at 95° C. under nitrogen for 29 h. The mixture was cooled to room temperature, filtered through celite, and the filter cake was washed with ethyl acetate (100 ml). The filtrate was concentrated and purified by column chromatography on silica (0-100% ethyl acetate in hexanes) to give 1,1-dimethylethyl 7-(2-methyl-1-{[(2-methylpropyl)oxy]carbonyl}-1H-imidazo[4,5-b]pyridine-6-yl)-2,3-dihydro-1,4-benzoxazepine-4(5H)carboxylate (1.1 g, 33% yield) as a yellow solid. 1H NMR (400 MHz, CDCl3): 8.74 (d, 1H), 8.39 (s, 1H), 7.47 (d, 1H), 7.43 (s, 1H), 7.14 (d, 1H), 4.50 (s, 2H), 4.34 (d, 2H), 4.12 (m, 2H), 3.88 (m, 2H), 2.96 (s, 3H), 2.22 (m, 1H), 1.42 (s, 9H), 1.21 (d, 6H); MS (EI) for C26H32N4O5: 481 (MH+).

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. filtrationfiltered through celite
  3. washthe filter cake was washed with ethyl acetate (100 ml)
  4. concentrationThe filtrate was concentrated
  5. custompurified by column chromatography on silica (0-100% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-e93b912058444f7db294ad4e8015fbd3
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08648066B2

反応ノート

読み込み中…

このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート