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

HRID 989045ノート

反応式

HRID 989045 の反応式
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

参加物

7

反応物 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

生成物 1

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

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

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%).

後処理

  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)

出典と根拠

ORDレコード
ord-423791d517d54030be8296c24d5d129d
出典データセット
uspto-grants-2003_10
特許番号
US06638934B2

反応ノート

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