Tri-o-tolylphosphine → HCID 54009539, 화합물

HRID 2305113노트

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HRID 2305113 반응식
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

참가 물질

8

반응물 4

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

생성물 1

HCID 54009539HCID 54009539, 화합물수율 42%

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 6342Acetonitrile용매HCID 8471Triethylamine용매

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온도
100 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-92cdd5c762ad4ba79cc1e5f7b730e6e5
출처 데이터셋
uspto-grants-2002_08
특허 번호
US06437138B1

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