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 516255노트

반응식

HRID 516255 반응식
[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

참가 물질

6

반응물 3

HCID 634876Binap, (A+-)-2회HCID 23676156Sodium t-butoxide2회HCID 58495302HCID 58495302, 화합물

생성물 1

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

시약·촉매·용매 2

HCID 9811564Bis(dibenzylideneacetone)palladium촉매2회HCID 1140Toluene용매

반응 조건

온도
100 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-f5566578c8604758814880f0bff960dc
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09108977B2

반응 노트

불러오는 중…