Chloride → HCID 71114821、化合物

HRID 1624038ノート

反応式

HRID 1624038 の反応式
[Cl-].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.[C:48]([C:50]1[CH:55]=[CH:54][C:53](B(O)O)=[CH:52][CH:51]=1)#[N:49].[CH3:59][CH:60]1[C:65](=[O:66])[CH:64]=[CH:63][CH2:62][CH2:61]1.C(=O)([O-])[O-].[K+].[K+]>C(O)(C)C.O1CCCC1>[CH3:59][C@H:60]1[CH2:61][CH2:62][C@H:63]([C:53]2[CH:54]=[CH:55][C:50]([C:48]#[N:49])=[CH:51][CH:52]=2)[CH2:64][C:65]1=[O:66].[CH3:59][C@@H:60]1[CH2:61][CH2:62][C@H:63]([C:53]2[CH:54]=[CH:55][C:50]([C:48]#[N:49])=[CH:51][CH:52]=2)[CH2:64][C:65]1=[O:66]

参加物

9

反応物 5

HCID 312ChlorideHCID 11430Potassium CarbonateHCID 634876Binap, (A+-)-HCID 27343264-Cyanophenylboronic acidHCID 110623356-Methylcyclohex-2-en-1-one

生成物 2

HCID 71114821HCID 71114821、化合物収率 22%HCID 71114860HCID 71114860、化合物収率 22%

試薬・触媒・溶媒 2

HCID 3776Isopropanol溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Bis(1,5-cyclooctadienerhodium chloride) (0.06 g, 0.12 mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.18 g, 0.29 mmol) are added to tetrahydrofuran (40 mL) and the mixture is stirred under a nitrogen atmosphere for 30 minutes. This solution is added to a mixture of 4-cyanophenylboronic acid (2.31 g, 15.69 mmol), 6-methylcyclohex-2-en-1-one (Journal of Organic Chemistry, 1980 45(10), 1852-1863) (1.28 g, 11.62 mmol), potassium carbonate (2.19 g, 15.69 mmol), and isopropyl alcohol (1.1 mL) at 60° C. The mixture is stirred at 60° C. for 16 hours and then concentrated to dryness. The crude mixture is poured into water (10 mL) and is extracted with ethyl acetate (2×20 mL). The organic extracts are dried over MgSO4, filtered through silica gel, and concentrated to dryness. The residue is purified by silica gel flash chromatography, eluting with 20% EtOAc/hexane to give (trans)-4-(4-methyl-3-oxo-cyclohexyl)benzonitrile (0.55 g, 22%) as the first eluting isomer and (cis)-4-(4-methyl-3-oxo-cyclohexyl)benzonitrile (0.55 g, 22%) as the second eluting isomer. ES/MS m/z 214 (M+H).

後処理

  1. stirringThe mixture is stirred at 60° C. for 16 hours
  2. concentrationconcentrated to dryness
  3. additionThe crude mixture is poured into water (10 mL)
  4. extractionis extracted with ethyl acetate (2×20 mL)
  5. dry with materialThe organic extracts are dried over MgSO4
  6. filtrationfiltered through silica gel
  7. concentrationconcentrated to dryness
  8. customThe residue is purified by silica gel flash chromatography
  9. washeluting with 20% EtOAc/hexane

出典と根拠

ORDレコード
ord-99b75ae895b44da9a2d5ed4e60ed4922
出典データセット
uspto-grants-2014_07
特許番号
US08778984B2

反応ノート

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