Sulfuric acid magnesium salt (1:1) → 5-((4aR,8aS)-3,3-dimethyldecahydroquinoxalin-1-yl)-1-methyl-1H-indole-2-carbonitrile

HRID 1528300ノート

反応式

HRID 1528300 の反応式
[CH3:1][C:2]1([CH3:12])[CH2:11][NH:10][C@@H:9]2[C@@H:4]([CH2:5][CH2:6][CH2:7][CH2:8]2)[NH:3]1.Br[C:14]1[CH:15]=[C:16]2[C:20](=[CH:21][CH:22]=1)[N:19]([CH3:23])[C:18]([C:24]#[N:25])=[CH:17]2.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[H+].[B-](F)(F)(F)F.CC([O-])(C)C.[Na+].[O-]S([O-])(=O)=O.[Mg+2]>CC([O-])=O.CC([O-])=O.[Pd+2].CCOC(C)=O.O.C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:12])[NH:3][C@H:4]2[C@H:9]([CH2:8][CH2:7][CH2:6][CH2:5]2)[N:10]([C:14]2[CH:15]=[C:16]3[C:20](=[CH:21][CH:22]=2)[N:19]([CH3:23])[C:18]([C:24]#[N:25])=[CH:17]3)[CH2:11]1

参加物

11

反応物 6

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 28118Tetrafluoroboric acidHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 66800071(4aS,8aR)-2,2-dimethyldecahydroquinoxalineHCID 668030375-Bromo-1-methylindole-2-carbonitrile

生成物 1

HCID 569450505-((4aR,8aS)-3,3-dimethyldecahydroquinoxalin-1-yl)-1-methyl-1H-indole-2-carbonitrile収率 46%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A toluene (4 ml) suspension of (4aS,8aR)-2,2-dimethyldecahydroquinoxaline (168 mg, 0.998 mmol), 5-bromo-1-methyl-1H-indole-2-carbonitrile (259 mg, 1.10 mmol), Pd(OAc)2 (11.2 mg, 0.0499 mmol), t-Bu3P.HBF4 (14.5 mg, 0.0500 mmol), and NaOt-Bu (135 mg, 1.40 mmol) was stirred for 4 hours under reflux in a nitrogen atmosphere. The reaction solution was cooled to room temperature. Then, water (0.5 mL) and AcOEt (10 mL) were added thereto, and the mixture was stirred. MgSO4 was further added thereto, and the mixture was stirred. Insoluble matter was filtered through celite, and the residue was washed with CH2Cl2:MeOH (3:1) (5 mL×2). Then, the filtrate was concentrated under reduced pressure. The obtained residue was purified by basic silica gel column chromatography (Hex-AcOEt) to obtain a colorless oil. This oil was crystallized from hexane (1 mL) to obtain 5-((4aR,8aS)-3,3-dimethyldecahydroquinoxalin-1-yl)-1-methyl-1H-indole-2-carbonitrile (148 mg, yield: 46%) in a pale yellow powder form.

後処理

  1. temperatureunder reflux in a nitrogen atmosphere
  2. stirringthe mixture was stirred
  3. filtrationInsoluble matter was filtered through celite
  4. washthe residue was washed with CH2Cl2:MeOH (3:1) (5 mL×2)
  5. concentrationThen, the filtrate was concentrated under reduced pressure
  6. customThe obtained residue was purified by basic silica gel column chromatography (Hex-AcOEt)
  7. customto obtain a colorless oil
  8. customThis oil was crystallized from hexane (1 mL)

出典と根拠

ORDレコード
ord-1812374078ba479ca7167ca4bba1db4b
出典データセット
uspto-grants-2015_07
特許番号
US09090572B2

反応ノート

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