Acrylonitrile → (+/-)-tert-butyl (1R,5S,65)-6-(2-cyanoethoxy)-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate

HRID 705291노트

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HRID 705291 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].[C:26](#[N:29])[CH:27]=[CH2:28].C(=O)([O-])[O-].[Cs+].[Cs+].C([O-])(O)=O.[Na+]>CC(O)(C)C.O>[C:26]([CH2:27][CH2:28][O:1][C@@H:2]1[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][C@@H:3]1[CH3:25])#[N:29]

참가 물질

7

반응물 4

HCID 7855AcrylonitrileHCID 10796Cesium carbonateHCID 516892Sodium BicarbonateHCID 86705242(+/-)-Tert-butyl (1R,5S,6S)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate

생성물 1

HCID 86705253(+/-)-tert-butyl (1R,5S,65)-6-(2-cyanoethoxy)-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate수율 94%

시약·촉매·용매 2

HCID 962Water용매HCID 6386tert-Butanol용매

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온도
35 °C

실험 절차

A mixture of (+/−)-Tert-butyl (1R,5S,65)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate (1.0 equiv.), acrylonitrile (30.0 equiv.) and CESIUM CARBONATE (1.2 equiv.) in t-BuOH (0.57 M) was stirred at 35° C. for 3 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 SiO2 chromatography to yield (+/−)-tert-butyl (1R,5S,6S)-6-(2-cyanoethoxy)-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate in 94% yield. LC/MS (m/z)=403.3 (MH+), Rt=0.92 min. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.13 (d, J=6.46 Hz, 3 H), 1.46 (s, 9 H), 1.99-2.18 (m, 2 H), 2.20-2.36 (m, 1 H), 2.65 (t, J=6.06 Hz, 2 H), 3.68 (br. s., 1 H), 3.88 (t, J=5.99 Hz, 2 H), 4.51 (br. s., 1 H), 4.99 (d, J=9.15 Hz, 1 H), 5.39 (br. s., 1 H), 7.25 (d, J=4.99 Hz, 1 H), 8.73 (d, J=4.94 Hz, 1 H), 9.10 (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 SiO2 chromatography

출처 및 근거

ORD 기록
ord-24fde94673cc43d991f9d235db9a9f2e
출처 데이터셋
uspto-grants-2015_11
특허 번호
US09173883B2

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