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

HRID 705297ノート

反応式

HRID 705297 の反応式
[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

参加物

7

反応物 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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6386tert-Butanol溶媒

反応条件

温度
22 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-060f093d756b4f95a468156b3dbc4b51
出典データセット
uspto-grants-2015_11
特許番号
US09173883B2

反応ノート

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