(3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-4-(nonafluorobutane-1-sulfonyloxy)-3,6-dihydro-2H-1,2-oxazine

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-4-(nonafluorobutane-1-sulfonyloxy)-3,6-dihydro-2H-1,2-oxazine
• 英文别名: [(3S)-2-benzyl-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3,6-dihydrooxazin-4-yl] 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate
• 化学式: C₂₀H₂₀F₉NO₆S
• 分子量: 573.434
• InChiKey: OKSKAMJKABENOI-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  82.7
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-4-(nonafluorobutane-1-sulfonyloxy)-3,6-dihydro-2H-1,2-oxazine 、 三甲基乙炔基硅 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 甲苯 为溶剂， 以80%的产率得到(3R,4'S)-2-benzyl-4-[trimethylsilyl(ethynyl)]-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-3,6-dihydro-2H-1,2-oxazine
  参考文献：
  名称：

  Convenient Syntheses of Enantiopure 1,2-Oxazin-4-yl Nonaflates and Phosphates and Their Palladium-Catalyzed Cross-Couplings

  摘要：

  Efficient methods to prepare enantiopure 1,2-oxazin-4-yl nonaflates and phosphates were elaborated. The corresponding 1,2-oxazin-4-ones were transformed into their enolates and then quenched with nonafluorobutanesulfonyl fluoride or diphenyl chlorophosphate to provide the title compounds. Alternatively, the corresponding -bromo ketones were subjected to Perkow reactions efficiently leading to the respective enol phosphates. A variety of palladium-catalyzed cross-couplings such as Kumada-Corriu, Sonogashira, Heck reactions or borylation reactions were studied, which delivered the expected new 4-substituted 1,2-oxazine derivatives generally in satisfactory yields. A few typical subsequent transformations were studied including a copper-catalyzed [3+2] cycloaddition with a galactose-derived azide. They demonstrate the synthetic potential of the newly prepared enantiopure 4-substituted 1,2-oxazines.

  DOI：

  10.1055/s-0033-1339509
• 作为产物：
  描述：

  (3S,4'S)-2-benzyl-4-benzyloxy-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-3,6-dihydro-2H-1,2-oxazine 在 钯 、 lithium hexamethyldisilazane 、 环己烯 作用下， 以 四氢呋喃 、 甲醇 、 乙酸乙酯 为溶剂， 反应 5.0h， 生成 (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-4-(nonafluorobutane-1-sulfonyloxy)-3,6-dihydro-2H-1,2-oxazine
  参考文献：
  名称：

  Convenient Syntheses of Enantiopure 1,2-Oxazin-4-yl Nonaflates and Phosphates and Their Palladium-Catalyzed Cross-Couplings

  摘要：

  Efficient methods to prepare enantiopure 1,2-oxazin-4-yl nonaflates and phosphates were elaborated. The corresponding 1,2-oxazin-4-ones were transformed into their enolates and then quenched with nonafluorobutanesulfonyl fluoride or diphenyl chlorophosphate to provide the title compounds. Alternatively, the corresponding -bromo ketones were subjected to Perkow reactions efficiently leading to the respective enol phosphates. A variety of palladium-catalyzed cross-couplings such as Kumada-Corriu, Sonogashira, Heck reactions or borylation reactions were studied, which delivered the expected new 4-substituted 1,2-oxazine derivatives generally in satisfactory yields. A few typical subsequent transformations were studied including a copper-catalyzed [3+2] cycloaddition with a galactose-derived azide. They demonstrate the synthetic potential of the newly prepared enantiopure 4-substituted 1,2-oxazines.

  DOI：

  10.1055/s-0033-1339509

文献信息

• Convenient Syntheses of Enantiopure 1,2-Oxazin-4-yl Nonaflates and Phosphates and Their Palladium-Catalyzed Cross-Couplings
  作者：Reinhold Zimmer、Hans-Ulrich Reissig、Nima Moinizadeh、Robby Klemme、Marcus Kansy

  DOI：10.1055/s-0033-1339509

  日期：——

  Efficient methods to prepare enantiopure 1,2-oxazin-4-yl nonaflates and phosphates were elaborated. The corresponding 1,2-oxazin-4-ones were transformed into their enolates and then quenched with nonafluorobutanesulfonyl fluoride or diphenyl chlorophosphate to provide the title compounds. Alternatively, the corresponding -bromo ketones were subjected to Perkow reactions efficiently leading to the respective enol phosphates. A variety of palladium-catalyzed cross-couplings such as Kumada-Corriu, Sonogashira, Heck reactions or borylation reactions were studied, which delivered the expected new 4-substituted 1,2-oxazine derivatives generally in satisfactory yields. A few typical subsequent transformations were studied including a copper-catalyzed [3+2] cycloaddition with a galactose-derived azide. They demonstrate the synthetic potential of the newly prepared enantiopure 4-substituted 1,2-oxazines.