Propionitrile → HCID 57470608、化合物

HRID 602061ノート

反応式

HRID 602061 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[C@H:9]([OH:12])[CH2:10][OH:11].C(#N)CC.[C:17]([O:21][CH2:22][CH3:23])(=[O:20])[CH:18]=[CH2:19].C(N(CC)CC)C.CC1C(P(C2C(C)=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1>CC([O-])=O.CC([O-])=O.[Pd+2].CCOC(C)=O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:19]=[CH:18]/[C:17]([O:21][CH2:22][CH3:23])=[O:20])=[CH:4][C:3]=1[C@H:9]([OH:12])[CH2:10][OH:11]

参加物

8

反応物 5

HCID 7854PropionitrileHCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 57470607(1S)-1-(2-chloro-5-iodophenyl)ethane-1,2-diol

生成物 1

HCID 57470608HCID 57470608、化合物収率 81%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

(1S)-1-(2-chloro-5-iodophenyl)ethane-1,2-diol (2.60 g, 8.71 mmol), propionitrile (87 mL), ethyl acrylate (1.24 mL, 11.32 mmol), and triethylamine (3.6 mL, 26.13 mmol) were combined and N2 was flushed through the solution for 10 minutes. Then Pd(OAc)2 (587 mg, 0.871 mmol) and P(O-tol)3 (1.06 g, 3.48 mmol) were added and the solution was heated to 80° C. After 16 h, the solution was cooled to rt and then EtOAc was added. The solution was washed with 1N HCl (2×), brine, dried, concentrated, and purified by Biotage chromatography (0%-100% EtOAc/hexanes) to afford 1.90 g of product as an oil (81%). 1H NMR (400 MHz, chloroform-d) δ ppm 7.79 (d, J=1.77 Hz, 1 H) 7.65 (d, J=16.17 Hz, 1 H) 7.34-7.40 (m, 2 H) 6.45 (d, J=15.92 Hz, 1 H) 5.24 (ddd, J=7.39, 2.84, 2.65 Hz, 1 H) 4.27 (q, J=7.24 Hz, 2 H) 3.89-3.97 (m, 1 H) 3.57 (ddd, J=11.49, 7.45, 4.55 Hz, 1 H) 2.87 (d, J=3.28 Hz, 1 H) 2.18 (t, J=5.81 Hz, 1 H) 2.05 (s, 3 H) 1.34 (t, J=7.20 Hz, 2 H).

後処理

  1. customN2 was flushed through the solution for 10 minutes
  2. temperaturethe solution was cooled to rt
  3. washThe solution was washed with 1N HCl (2×), brine
  4. customdried
  5. concentrationconcentrated
  6. custompurified by Biotage chromatography (0%-100% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-daa56d881f2c41878d0c63df863066a7
出典データセット
uspto-grants-2011_03
特許番号
US07902394B2

反応ノート

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