Binap, (A+-)- → ethyl (3R)-3-methyl-3,4,6,7,9,10-hexahydro[1,4]oxazino[2,3-h][3]benzazepine-8(2H)-carboxylate

HRID 516255ノート

反応式

HRID 516255 の反応式
[NH2:1][C@H:2]([CH3:22])[CH2:3][O:4][C:5]1[C:20](Br)=[CH:19][C:8]2[CH2:9][CH2:10][N:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:12][CH2:13][C:7]=2[CH:6]=1.CC(C)([O-])C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:22][C@@H:2]1[CH2:3][O:4][C:5]2[C:20](=[CH:19][C:8]3[CH2:9][CH2:10][N:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:12][CH2:13][C:7]=3[CH:6]=2)[NH:1]1

参加物

6

反応物 3

HCID 634876Binap, (A+-)-2 回HCID 23676156Sodium t-butoxide2 回HCID 58495302HCID 58495302、化合物

生成物 1

HCID 66982702ethyl (3R)-3-methyl-3,4,6,7,9,10-hexahydro[1,4]oxazino[2,3-h][3]benzazepine-8(2H)-carboxylate収率 47.6%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒2 回HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

Under an argon atmosphere, to a solution of 1.64 g of ethyl 7-{[(2R)-2-aminopropyl]oxy}-8-bromo-1,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxylate in 41 ml of toluene were added 509 mg of sodium t-butoxide, 275 mg of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and 202 mg of tris(dibenzylideneacetone)dipalladium (0) in this order, followed by heating at 100° C. for 24 hours. Further, 509 mg of sodium t-butoxide, 275 mg of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and 202 mg of tris(dibenzylideneacetone)dipalladium (0) were added thereto, followed by stirring at 100° C. for additional 24 hours. The reaction mixture was returned to room temperature, then filtered through celite, and washed with ethyl acetate, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel chromatography (elution solvent: Hex-AcOEt) to obtain 610 mg of ethyl (3R)-3-methyl-3,4,6,7,9,10-hexahydro[1,4]oxazino[2,3-h][3]benzazepine-8(2H)-carboxylate.

後処理

  1. customwas returned to room temperature
  2. filtrationfiltered through celite
  3. washwashed with ethyl acetate
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was purified by silica gel chromatography (elution solvent: Hex-AcOEt)

出典と根拠

ORDレコード
ord-f5566578c8604758814880f0bff960dc
出典データセット
uspto-grants-2015_08
特許番号
US09108977B2

反応ノート

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