Triphenylphosphine → 1-Benzyl 4-tert-butyl 2-(2-(pyridin-3-yl)ethyl)piperazine-1,4-dicarboxylate

HRID 70132노트

반응식

HRID 70132 반응식
C12BC(CCC1)CCC2.[CH:10]([CH:12]1[CH2:17][N:16]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:15][CH2:14][N:13]1[C:25]([O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)=[O:26])=[CH2:11].Br[C:36]1[CH:37]=[N:38][CH:39]=[CH:40][CH:41]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[OH-].[Na+]>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[N:38]1[CH:39]=[CH:40][CH:41]=[C:36]([CH2:11][CH2:10][CH:12]2[CH2:17][N:16]([C:18]([O:20][C:21]([CH3:24])([CH3:22])[CH3:23])=[O:19])[CH2:15][CH2:14][N:13]2[C:25]([O:27][CH2:28][C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)=[O:26])[CH:37]=1

참가 물질

7

반응물 5

HCID 11776TriphenylphosphineHCID 122863-BromopyridineHCID 14798Sodium HydroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 596714681-Benzyl 4-tert-butyl 2-vinylpiperazine-1,4-dicarboxylate

생성물 1

HCID 596715351-Benzyl 4-tert-butyl 2-(2-(pyridin-3-yl)ethyl)piperazine-1,4-dicarboxylate수율 63%

시약·촉매·용매 1

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매

실험 절차

9-Borabicyclo[3.3.1]nonane (0.5M solution in THF, 54 mL, 27 mmol) was added to 1-benzyl 4-tert-butyl 2-vinylpiperazine-1,4-dicarboxylate (2.33 g, 6.73 mmol). After 3 h, 3-bromopyridine (0.99 mL, 10.1 mmol), triphenylphosphine (0.53 g, 2.0 mmol), and tetrakis(triphenylphosphine) palladium(0) (0.311 g, 0.27 mmol) were added. Sodium hydroxide (1N aqueous solution, 16.8 mL, 16.8 mmol) was added slowly. Once bubbling ceased, the reaction mixture was heated to reflux overnight. Upon cooling to rt, the reaction mixture was diluted with water (200 mL) and extracted with EtOAc (3×200 mL). The combined organics were dried over Na2SO4, filtered, and concentrated under reduced pressure. Purification by column chomatography (10 to 40% EtOAc in Hexane gradient) gave 1.79 g (63%) of the desired product as a thick oil. Rf=0.57 in 80% EtOAc/Hexane. LC-MS: RT=7.69 min., [M+H]+=426.2. The material was contaminated with ˜15% triphenylphosphine, and was used without further purification.

후처리

  1. customOnce bubbling
  2. temperaturethe reaction mixture was heated
  3. temperatureto reflux overnight
  4. additionthe reaction mixture was diluted with water (200 mL)
  5. extractionextracted with EtOAc (3×200 mL)
  6. dry with materialThe combined organics were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customPurification by column chomatography (10 to 40% EtOAc in Hexane gradient)

출처 및 근거

ORD 기록
ord-627ca709717e4dec9abccce2d49a3424
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08822472B2

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