Water → (4R,9aR)-6-Ethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic Acid Tert-butyl Ester

HRID 11916

反応式

HRID 11916 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15](Br)=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:23](B(CC)CC)[CH3:24].C(=O)([O-])[O-].[K+].[K+].O>CN(C)C=O.C1COCC1.Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH2:23][CH3:24])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

8

反応物 4

HCID 962WaterHCID 7357Triethylborane2 回HCID 11430Potassium CarbonateHCID 86590113(4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester2 回

生成物 1

HCID 69359739(4R,9aR)-6-Ethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic Acid Tert-butyl Ester収率 89.5%

試薬・触媒・溶媒 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of 0.70 g (1.90 mmol) (4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (Example 5, intermediate b) in 14 ml N,N-dimethylformamide was added 73.0 mg [1,1′-bis(diphenyphosphino)ferrocene]-dichloropalladium(II) and after 15 min, 4.8 ml of a 1M triethylborane solution in THF and 0.79 g (5.70 mmol) potassium carbonate were added. After 4 h another 2.4 ml triethylborane solution was added and the reaction mixture stirred overnight at 65 deg C. The mixture was cooled to room temperature and the suspension was poured into water and extracted twice with ethyl acetate. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered and evaporated. The crude product was purified by column chromatography on silica gel (Q0.032–0.063 mm) with tert-butyl methyl ether:n-hexane (1:4) as eluant to yield the product as a colorless oil (89.5%).

後処理

  1. extractionextracted twice with ethyl acetate
  2. washThe combined organic phases were washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customThe crude product was purified by column chromatography on silica gel (Q0.032–0.063 mm) with tert-butyl methyl ether:n-hexane (1:4) as eluant

出典と根拠

ORDレコード
ord-e401693ea07b49d8b2d0052599bf9d7b
出典データセット
uspto-grants-2006_08
特許番号
US07098337B2

関連ノート

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