Cesium carbonate → (+/-)-tert-butyl (1R,5S,6S)-5-methyl-6-(2-(methylsulfonyl)ethoxy)-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate

HRID 705297노트

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HRID 705297 반응식
[OH:1][C@@H:2]1[C@H:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=[C:5]([C:16]2[CH:21]=[CH:20][N:19]=[CH:18][C:17]=2[N+:22]([O-:24])=[O:23])[CH2:4][C@@H:3]1[CH3:25].[CH3:26][S:27]([CH:30]=[CH2:31])(=[O:29])=[O:28].C(=O)([O-])[O-].[Cs+].[Cs+].C([O-])(O)=O.[Na+]>CC(O)(C)C.O>[CH3:25][C@@H:3]1[C@H:2]([O:1][CH2:31][CH2:30][S:27]([CH3:26])(=[O:29])=[O:28])[C@H:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:12])([CH3:13])[CH3:14])[CH:6]=[C:5]([C:16]2[CH:21]=[CH:20][N:19]=[CH:18][C:17]=2[N+:22]([O-:24])=[O:23])[CH2:4]1

참가 물질

7

반응물 4

HCID 10796Cesium carbonateHCID 19354Methyl vinyl sulfoneHCID 516892Sodium BicarbonateHCID 86705242(+/-)-Tert-butyl (1R,5S,6S)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate

생성물 1

HCID 86705262(+/-)-tert-butyl (1R,5S,6S)-5-methyl-6-(2-(methylsulfonyl)ethoxy)-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate수율 84%

시약·촉매·용매 2

HCID 962Water용매HCID 6386tert-Butanol용매

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온도
22 °C

실험 절차

A mixture of (+/−)-Tert-butyl (1R,5 S,65)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate (1.0 equiv.), methylsulfonylethene (30.0 equiv.) and CESIUM CARBONATE (1.2 equiv.) in t-BuOH (0.22 M) was stirred at 22° C. for 5 hrs. The reaction was cooled to room temperature, followed by the addition of NaHCO3(aq) and water. The mixture was extracted with EtOAc and the combined organics were dried over MgSO4, filtered, and concentrated. The sample was purified by ISCO chromatography to yield (+/−)-tert-butyl (1R,5S,6S)-5-methyl-6-(2-(methylsulfonyl)ethoxy)-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate in 84% yield. LC/MS (m/z)=456.2 (MH+), Rt=0.87 min. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.10 (d, J=6.60 Hz, 3 H), 1.47 (s, 9 H), 1.92-2.16 (m, 2 H), 2.17-2.32 (m, 1 H), 2.93-3.00 (m, 1 H), 3.09 (s, 3 H), 3.18 (d, J=14.87 Hz, 1 H), 3.38-3.52 (m, 1 H), 3.63 (d, J=2.40 Hz, 1 H), 3.95-4.06 (m, 1 H), 4.21 (td, J=9.84, 2.42 Hz, 1 H), 4.56 (d, J=7.58 Hz, 1 H), 5.58 (br. s., 1 H), 5.66 (d, J=9.44 Hz, 1 H), 7.20 (d, J=4.99 Hz, 1 H), 8.73 (d, J=4.99 Hz, 1 H), 9.05 (s, 1 H).

후처리

  1. temperatureThe reaction was cooled to room temperature
  2. extractionThe mixture was extracted with EtOAc
  3. dry with materialthe combined organics were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe sample was purified by ISCO chromatography

출처 및 근거

ORD 기록
ord-060f093d756b4f95a468156b3dbc4b51
출처 데이터셋
uspto-grants-2015_11
특허 번호
US09173883B2

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