홈MCP워크벤치Skills
홈워크벤치알림마이페이지
llms.txt · MCP 가이드개인정보처리방침 · 이용약관 · 지원v1.8.0
  1. 홈
  2. /반응

Phenyl triflimide → (+/-)-tert-Butyl-2-({[tert-butyl(diphenyl)silyl]oxy}methyl)-3-(2,5-difluorophenyl)-5-phenyl-2,5-dihydro-1H-pyrrole-1-carboxylate

HRID 32857
노트
인쇄 미리보기

반응식

HRID 32857 반응식
[C:1]([O:5][C:6]([N:8]1[CH:12]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:11][CH:10](O)[CH:9]1[CH2:20][O:21][Si:22]([C:35]([CH3:38])([CH3:37])[CH3:36])([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].N(C1C=CC=CC=1)(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O.[F:92][C:93]1[CH:98]=[CH:97][C:96]([F:99])=[CH:95][C:94]=1B(O)O>C(Cl)Cl.C1COCC1.CCOC(C)=O.O1CCOCC1.C([O-])([O-])=O.[Na+].[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>[C:1]([O:5][C:6]([N:8]1[CH:12]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:11]=[C:10]([C:94]2[CH:95]=[C:96]([F:99])[CH:97]=[CH:98][C:93]=2[F:92])[CH:9]1[CH2:20][O:21][Si:22]([C:35]([CH3:38])([CH3:37])[CH3:36])([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

12

반응물 5

HCID 142176Phenyl triflimideHCID 159087TriacetoxyperiodinaneHCID 2724254Sodium bis(trimethylsilyl)amideHCID 2734335(2,5-Difluorophenyl)boronic acidHCID 71026194(+/-)-tert-Butyl-2-({[tert-butyl(diphenyl)silyl]oxy}methyl)-3-hydroxy-5-phenylpyrrolidine-1-carboxylate

생성물 1

HCID 68887446
(+/-)-tert-Butyl-2-({[tert-butyl(diphenyl)silyl]oxy}methyl)-3-(2,5-difluorophenyl)-5-phenyl-2,5-dihydro-1H-pyrrole-1-carboxylate

시약·촉매·용매 6

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매2회HCID 8857Ethyl Acetate용매2회HCID 10340Sodium Carbonate용매HCID 312751,4-Dioxane용매

실험 절차

A solution of the carbinol 1-6 (36 g, 67.7 mmol) in CH2Cl2 (400 mL) was treated with Dess-Martin periodinane (29 g, 67.7 mmol). After stirring for 1 h at rt the reaction was quenched with a 1:1 (200 mL) solution of Na2S2O3/NaHCO3 and the mixture stirred vigorously for 2 h. The reaction was extracted with CH2Cl2 (2×200 mL) and the combined organic solutions dried over MgSO4, filtered, and concentrated. The residue (35.5 g, 67.0 mmol) was dissolved in THF (500 mL) and cooled to −78° C. The solution was treated with NaHMDS (83.0 mL of a 1M soln in THF, 83 mmol) and stirred at −78° C. for 1 h. Neat Tf2NPh (28.7 g, 80.4 mmol) was added to the reaction and the reaction was stirred with gradual warming to rt for 12 h. The reaction was diluted with EtOAc and washed with satd aq NH4Cl and brine. The organic solution was dried over MgSO4, filtered and concentrated. The residue (44.3 g, 66.9 mmol) was dissolved in dioxane (300 mL) and 2M Na2CO3 (100 mL). The mixture was degassed with a flow of N2 (g) for 30 min and treated with 2,5-difluorophenylboronic acid (13.7 g, 87 mmol) and tetrakis(triphenylphosphine)-palladium (3.8 g, 3.3 mmol). The yellow mixture was heated at 90° C. for 90 min, cooled to rt, and diluted with EtOAc (300 mL). The organic solution was washed with satd aq NH4Cl (150 mL), dried over MgSO4, filtered, and concentrated. The residue was purified by flash chromatography (SiO2; 20/80 CH2Cl2/hexanes to 10% EtOAc/hexanes) to provide the desired product diastereomers 1-7 as a yellow foam. LRMS (m/z) M+1 expected 627, found 627.

후처리

  1. customwas quenched with a 1:1 (200 mL) solution of Na2S2O3/NaHCO3
  2. stirringthe mixture stirred vigorously for 2 h
  3. extractionThe reaction was extracted with CH2Cl2 (2×200 mL)
  4. dry with materialthe combined organic solutions dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. temperaturecooled to −78° C
  8. stirringstirred at −78° C. for 1 h
  9. stirringthe reaction was stirred
  10. temperaturewith gradual warming to rt for 12 h
  11. washwashed with satd aq NH4Cl and brine
  12. dry with materialThe organic solution was dried over MgSO4
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customThe mixture was degassed with a flow of N2 (g) for 30 min
  16. temperatureThe yellow mixture was heated at 90° C. for 90 min
  17. temperaturecooled to rt
  18. washThe organic solution was washed with satd aq NH4Cl (150 mL)
  19. dry with materialdried over MgSO4
  20. filtrationfiltered
  21. concentrationconcentrated
  22. customThe residue was purified by flash chromatography (SiO2; 20/80 CH2Cl2/hexanes to 10% EtOAc/hexanes)

출처 및 근거

ORD 기록
ord-2bca8717096c479bb0a9f40dce1fb5e6
출처 데이터셋
uspto-grants-2008_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07427637B2

반응 노트

불러오는 중…

이 페이지에서참가 물질실험 절차후처리출처 및 근거반응 노트