(4S)-4-benzyl-3-[(2R)-2-bromopropanoyl]-1,3-oxazolidin-2-one | 114341-80-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4S)-4-benzyl-3-[(2R)-2-bromopropanoyl]-1,3-oxazolidin-2-one
• CAS: 114341-80-9
• 化学式: C₁₃H₁₄BrNO₃
• 分子量: 312.163
• InChiKey: WMEFKODGDLZACH-KOLCDFICSA-N

物化性质

• 沸点：
  430.0±28.0 °C(predicted)
• 密度：
  1.508±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S)-4-benzyl-3-[(2R)-2-bromopropanoyl]-1,3-oxazolidin-2-one 在 偶氮二异丁腈 、 三乙基硼 、 三(三甲基硅基)硅烷 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 正己烷 、 1,2-二氯乙烷 、 苯 为溶剂， 反应 3.0h， 生成 2-methyloctanoyl (5(S)-benzyl-2-oxazolidone) amide
  参考文献：
  名称：

  Lewis Acid-Promoted Atom-Transfer Free Radical Additions

  摘要：

  The reactions of alpha-bromo oxazolidinone imides of acetic and propionic acid and terminal and internal alkenes were investigated in the presence of Lewis acids. Thus, the primary bromide, bromoacetyl-2-oxazolidinone amide (1), undergoes clean atom-transfer addition to 1-hexene as well as cis- or trans-3-hexene at room temperature or below. The best Lewis acids for this conversion are Sc(Otf)(3) and Yb(Otf)(3). Quantitative yields are obtained with Yb(Otf)(3) for addition of the bromide to both 1-hexene and cis-3-hexene, while the yield with trans-3-hexene is 63%. Yields obtained with Sc(Otf)(3) are somewhat lower. The effects of solvent, temperature, and Lewis acid loading have been investigated. The secondary bromide, alpha-bromoproprionyl-2-oxazolidinone amide (7), was also investigated in atom-transfer addition to 1-hexene. Yields are comparable to those in the reaction of 1 with 1-hexene, but internal alkenes fail to react with this substrate. Tertiary bromides do not react with any of the alkenes studied. Control of stereochemistry in the atom-transfer addition is possible by the use of chiral auxiliary oxazolidinones. Thus, the benzyl oxazolidinone and isopropyl analogue give excellent control of configuration in the new stereogenic center generated in the addition of the propionate to 1-hexene. Attempts to achieve enantioselective atom-transfer addition fail to give product in high yield or stereoselectivity.

  DOI：

  10.1021/ja990477e
• 作为产物：
  描述：

  (S)-4-苄基-2-唑烷酮 、 2-溴丙酰溴 在 正丁基锂 作用下， 生成 (4S)-4-benzyl-3-[(2S)-2-bromopropanoyl]-1,3-oxazolidin-2-one 、 (4S)-4-benzyl-3-[(2R)-2-bromopropanoyl]-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Indole Inhibitors of Human Nonpancreatic Secretory Phospholipase A₂. 3. Indole-3-glyoxamides

  摘要：

  The preceding papers of this series detail the development of functionalized indole-3-acetamides as inhibitors of hnps-PLA(2). We describe here the extension of the structure-activity relationship to include a series of indole-3-glyoxamide derivatives. Functionalized indole-3-glyoxamides with an acidic substituent appended to the 4- or 5-position of the indole ring were prepared and tested as inhibitors of hnps-PLA(2). It was found that the indole-3-glyoxamides with a 4-oxyacetic acid substituent had optimal inhibitory activity. These inhibitors exhibited an improvement in potency over the best of the indole-3-acetamides, and LY315920 (6m) was selected for evaluation clinically as an hnps-PLA(2) inhibitor.

  DOI：

  10.1021/jm960487f

文献信息

• Electron-Transfer Photoredox Catalysis: Development of a Tin-Free Reductive Dehalogenation Reaction
  作者：Jagan M. R. Narayanam、Joseph W. Tucker、Corey R. J. Stephenson

  DOI：10.1021/ja9033582

  日期：2009.7.1

  We report an operationally simple, tin-free reductive dehalogenation system utilizing the well-known visible-light-activated photoredox catalyst Ru(bpy)(3)Cl(2) in combination with (i)Pr(2)NEt and HCO(2)H or Hantzsch ester as the hydrogen atom donor. Activated C-X bonds may be reduced in good yields with excellent functional-group tolerance and chemoselectivity over aryl and vinyl C-X bonds. The proposed

  我们报告了一种操作简单、无锡的还原脱卤系统，该系统利用众所周知的可见光活化光氧化还原催化剂 Ru(bpy)(3)Cl(2) 结合 (i)Pr(2)NEt 和 HCO(2) )H 或 Hantzsch 酯作为氢原子供体。与芳基和乙烯基 CX 键相比，活化的 CX 键可以以良好的收率减少，具有优异的官能团耐受性和化学选择性。所提出的机制涉及催化剂的可见光激发，其被叔胺还原以产生单电子还原剂 Ru(bpy)(3)(+)。随后的单电子转移产生烷基自由基，该自由基通过夺取一个氢原子而猝灭。使用低至 0.05 mol% 的 Ru 催化剂就可以在制备规模上完成还原。
• Indole Inhibitors of Human Nonpancreatic Secretory Phospholipase A₂. 3. Indole-3-glyoxamides
  作者：Susan E. Draheim、Nicholas J. Bach、Robert D. Dillard、Dennis R. Berry、Donald G. Carlson、Nickolay Y. Chirgadze、David K. Clawson、Lawrence W. Hartley、Lea M. Johnson、Noel D. Jones、Emma R. McKinney、Edward D. Mihelich、Jennifer L. Olkowski、Richard W. Schevitz、Amy C. Smith、David W. Snyder、Cynthia D. Sommers、Jean-Pierre Wery

  DOI：10.1021/jm960487f

  日期：1996.1.1

  The preceding papers of this series detail the development of functionalized indole-3-acetamides as inhibitors of hnps-PLA(2). We describe here the extension of the structure-activity relationship to include a series of indole-3-glyoxamide derivatives. Functionalized indole-3-glyoxamides with an acidic substituent appended to the 4- or 5-position of the indole ring were prepared and tested as inhibitors of hnps-PLA(2). It was found that the indole-3-glyoxamides with a 4-oxyacetic acid substituent had optimal inhibitory activity. These inhibitors exhibited an improvement in potency over the best of the indole-3-acetamides, and LY315920 (6m) was selected for evaluation clinically as an hnps-PLA(2) inhibitor.
• Lewis Acid-Promoted Atom-Transfer Free Radical Additions
  作者：Christopher L. Mero、Ned A. Porter

  DOI：10.1021/ja990477e

  日期：1999.6.1

  The reactions of alpha-bromo oxazolidinone imides of acetic and propionic acid and terminal and internal alkenes were investigated in the presence of Lewis acids. Thus, the primary bromide, bromoacetyl-2-oxazolidinone amide (1), undergoes clean atom-transfer addition to 1-hexene as well as cis- or trans-3-hexene at room temperature or below. The best Lewis acids for this conversion are Sc(Otf)(3) and Yb(Otf)(3). Quantitative yields are obtained with Yb(Otf)(3) for addition of the bromide to both 1-hexene and cis-3-hexene, while the yield with trans-3-hexene is 63%. Yields obtained with Sc(Otf)(3) are somewhat lower. The effects of solvent, temperature, and Lewis acid loading have been investigated. The secondary bromide, alpha-bromoproprionyl-2-oxazolidinone amide (7), was also investigated in atom-transfer addition to 1-hexene. Yields are comparable to those in the reaction of 1 with 1-hexene, but internal alkenes fail to react with this substrate. Tertiary bromides do not react with any of the alkenes studied. Control of stereochemistry in the atom-transfer addition is possible by the use of chiral auxiliary oxazolidinones. Thus, the benzyl oxazolidinone and isopropyl analogue give excellent control of configuration in the new stereogenic center generated in the addition of the propionate to 1-hexene. Attempts to achieve enantioselective atom-transfer addition fail to give product in high yield or stereoselectivity.