Sodium Chloride → tert-butyl ((3S,7S,8R,9S)-7-benzyl-9-methyl-2-oxo-8-phenoxy-1,5-dioxonan-3-yl)carbamate

HRID 75756

反応式

HRID 75756 の反応式
[CH2:1]([C@@H:8]1[C@@H:16]([OH:17])[C@H:15]([CH3:18])[O:14][C:13](=[O:19])[C@@H:12]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.FC(F)(F)S(O[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[Si](C)(C)C)(=O)=O.[F-].[Cs+].[Na+].[Cl-]>CC#N>[CH2:1]([C@@H:8]1[C@@H:16]([O:17][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C@H:15]([CH3:18])[O:14][C:13](=[O:19])[C@@H:12]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

6

反応物 4

HCID 5234Sodium ChlorideHCID 25953Cesium fluorideHCID 33840072-(Trimethylsilyl)phenyl trifluoromethanesulfonateHCID 86701245tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate

生成物 1

HCID 86701251tert-butyl ((3S,7S,8R,9S)-7-benzyl-9-methyl-2-oxo-8-phenoxy-1,5-dioxonan-3-yl)carbamate収率 11.5%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

To a solution of tert-butyl ((3S,7S,8R,9S)-7-benzyl-8-hydroxy-9-methyl-2-oxo-1,5-dioxonan-3-yl)carbamate (500 mg, 1.32 mmol, 1.00 equiv) in anhydrous CH3CN (13 mL) were added 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.480 mL, 1.98 mmol, 1.50 equiv) followed by CsF (500 mg, 3.29 mmol, 2.50 equiv). The resulting mixture was stirred at room temperature for 2 d. The reaction was then poured into ½ sat'd NaCl solution (20 mL), extracted with EtOAc (3×20 mL), and the combined organic extracts were dried over MgSO4, filtered, and concentrated to provide an oily yellow suspension. This was purified by automated silica gel column chromatograpy to provide tert-butyl ((3S,7S,8R,9S)-7-benzyl-9-methyl-2-oxo-8-phenoxy-1,5-dioxonan-3-yl)carbamate (69 mg, 11%) as an amorphous light yellow solid: 1H NMR (400 MHz, CDCl3) δ 7.34-7.20 (m, 5H), 7.20-7.04 (m, 4H), 7.02-6.88 (d, J=8.7 Hz, 4H), 5.20-5.02 (dq, J=9.1, 6.4 Hz, 2H), 4.71-4.57 (m, 1H), 4.37-4.21 (t, J=8.9 Hz, 1H), 4.00-3.88 (dd, J=11.6, 7.3 Hz, 1H), 3.60-3.44 (s, 2H), 3.38-3.21 (m, 1H), 3.07-2.93 (dd, J=13.6, 3.1 Hz, 1H), 2.37-2.21 (t, J=12.5 Hz, 1H), 2.22-2.09 (m, 1H), 1.46-1.40 (s, 9H), 1.40-1.34 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 172.29, 159.20, 154.98, 139.50, 129.75, 129.11, 128.42, 126.19, 121.34, 115.48, 81.96, 80.19, 75.39, 72.88, 72.08, 52.98, 47.56, 35.29, 28.29, 18.98; ESIMS m/z 478.6 ([M+Na]+).

後処理

  1. extractionextracted with EtOAc (3×20 mL)
  2. dry with materialthe combined organic extracts were dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customto provide an oily yellow suspension
  6. customThis was purified by automated silica gel column chromatograpy

出典と根拠

ORDレコード
ord-f1d0d59e478143e0904373747c3052b7
出典データセット
uspto-grants-2014_09
特許番号
US08835462B2

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