Tri-o-tolylphosphine → HCID 54009539、化合物

HRID 2305113ノート

反応式

HRID 2305113 の反応式
Br[C:2]1[CH:3]=[C:4]([O:9][CH2:10][C@H:11]2[CH2:15][CH2:14][CH2:13][N:12]2[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:5]=[N:6][C:7]=1Cl.[CH3:23][C:24]([CH3:30])([CH3:29])[CH:25]=[CH:26][CH:27]=[CH2:28].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)(O)[O-].[Na+]>C(#N)C.C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:23][C:24]([CH3:30])([CH3:29])[CH:25]=[CH:26][CH:27]=[CH:28][C:2]1[CH:3]=[C:4]([O:9][CH2:10][C@H:11]2[CH2:15][CH2:14][CH2:13][N:12]2[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH:5]=[N:6][CH:7]=1

参加物

8

反応物 4

HCID 80271Tri-o-tolylphosphineHCID 1420695,5-Dimethyl-1,3-hexadieneHCID 516892Sodium BicarbonateHCID 22872666HCID 22872666、化合物

生成物 1

HCID 54009539HCID 54009539、化合物収率 42%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 6342Acetonitrile溶媒HCID 8471Triethylamine溶媒

反応条件

温度
100 °C

実験手順

To a solution of 5-bromo-6-chloro-3-(1-BOC-2-(R)-pyrrolidinylmethoxy)pyridine (600 mg, 1.59 mmol) in acetonitrile (5.0 mL) and triethylamine (4.5 mL) was added 5,5-dimethyl-1,3-hexadiene (228 mg), palladium acetate (39 mg) and tri-o-tolylphosphine (205 mg). After being heated in a sealed tube at 100° C. overnight, the resulting mixture was cooled to room temperature. Minimum amount of saturated sodium bicarbonate was added to free the amine hydrochloride salt, and the mixture was extracted with EtOAc, dried (MgSO4), and concentrated. The residue was chromatographed on a silica gel column, eluting with EtOAc:hexane 1:3 to afford the title compound (126 mg, 42% yield). MS (CI/NH3) m/z 307 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ: 1.42 (s, 9H), 1.55 (s, 9H), 2.24-2.42 (m, 2H), 3.88 (t, J=7.5, 2H), 4.13 (dd, J=3, 7.5, 1H), 4.29-4.41 (m, 1H), 5.97 (d, J=15, 1H), 6.22 (dd, J=9, 15, 1H), 6.67-6.78 (m, 2H), 7.45 (br s, 1H), 8.95 (d, J=3.0, 1H).

後処理

  1. temperaturethe resulting mixture was cooled to room temperature
  2. extractionthe mixture was extracted with EtOAc
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customThe residue was chromatographed on a silica gel column
  6. washeluting with EtOAc:hexane 1:3

出典と根拠

ORDレコード
ord-92cdd5c762ad4ba79cc1e5f7b730e6e5
出典データセット
uspto-grants-2002_08
特許番号
US06437138B1

反応ノート

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