Tolylboronic acid → 9-(4-methylphenyl)-2,3,4,4a,5,6-hexahydro-1H-pyrazino[1,2-a]quinoxaline

HRID 989045노트

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HRID 989045 반응식
C1(P(C2CCCCC2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[C:14]2C=CC=CC=2N(C)C)CCCCC1.B(O)(O)C1C=CC(C)=CC=1.[F-].[K+].Cl[C:42]1[CH:51]=[C:50]2[C:45]([NH:46][CH2:47][CH:48]3[CH2:55][N:54](C(OCC4C=CC=CC=4)=O)[CH2:53][CH2:52][N:49]32)=[CH:44][CH:43]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[CH3:14][C:9]1[CH:10]=[CH:11][C:12]([C:42]2[CH:51]=[C:50]3[C:45]([NH:46][CH2:47][CH:48]4[CH2:55][NH:54][CH2:53][CH2:52][N:49]43)=[CH:44][CH:43]=2)=[CH:13][CH:8]=1

참가 물질

7

반응물 4

HCID 79799Tolylboronic acidHCID 522689Potassium FluorideHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 121094749-Chloro-3-carbobenzyloxy-2,3,4,4a,5,6-hexahydro-1H-pyrazino[1,2-a]quinoxaline

생성물 1

HCID 99003229-(4-methylphenyl)-2,3,4,4a,5,6-hexahydro-1H-pyrazino[1,2-a]quinoxaline수율 786.3%

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

To a two-necked round bottom flask charged with argon was added palladium (II) acetate (4 mg, 0.0195 mmol), 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl (10 mg, 0.02925 mmol), p-tolylboronic acid (80 mg, 0.59 mmol), potassium fluoride (68 mg, 1.17 mmol), and 9-Chloro-3-carbobenzyloxy-2,3,4,4a,5,6-hexahydro-1H-pyrazino[1,2-a]quinoxaline (140 mg, 0.39 mmol). 1 ml of degassed 1,4-dioxane was added and the reaction was degassed and heated to 100° C. for 20 h. The reaction mixture was cooled to rt and diluted with ether. 1N NaOH was added and the aqueous layer was extracted with ethyl acetate. The combined organics were washed with brine, dried over MgSO4, and concentrated to a yellow residue. The crude material was purified by radial PLC (1 mm plate, load with methylene chloride, elute with 20-40% ethyl acetate/hexanes) to give 9-(4-methylphenyl)-2,3,4,4a,5,6-hexahydro-1H-pyrazino[1,2-a]quinoxaline as a yellow foam (0.23 mmol, 60%).

후처리

  1. additionTo a two-necked round bottom flask charged with argon
  2. customthe reaction was degassed
  3. temperatureThe reaction mixture was cooled to rt
  4. additiondiluted with ether
  5. addition1N NaOH was added
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. washThe combined organics were washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated to a yellow residue
  10. customThe crude material was purified by radial PLC (1 mm plate, load with methylene chloride, elute with 20-40% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-423791d517d54030be8296c24d5d129d
출처 데이터셋
uspto-grants-2003_10
특허 번호
US06638934B2

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