Ethyl 2-bromo-2-methyl-3-methoxy-3-phenylpropionate | 153644-98-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ethyl 2-bromo-2-methyl-3-methoxy-3-phenylpropionate
• 英文别名: Ethyl 2-bromo-3-methoxy-2-methyl-3-phenylpropanoate
• CAS: 153644-98-5
• 化学式: C₁₃H₁₇BrO₃
• 分子量: 301.18
• InChiKey: QMUGCXOGRQWORK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ethyl 2-bromo-2-methyl-3-methoxy-3-phenylpropionate 在 三正丁基氢锡 、 六正丁基二锡 作用下， 生成 Ethyl erythro-3-methoxy-2-methyl-3-phenylpropanoate 、 Ethyl threo-3-methoxy-2-methyl-3-phenylpropanoate
  参考文献：
  名称：

  极性取代基对烯醇式自由基构象和立体化学的影响

  摘要：

  ESR测量和AM1计算表明，由于烯丙基应变效应，酯取代的基团2和6更偏爱构象A。但是，取代基X和CO 2 Et In 2和6之间的偶极排斥力对自由基2和6的构象和立体选择性具有显着影响。

  DOI：

  10.1016/s0040-4039(00)73805-6
• 作为产物：
  描述：

  苯甲醛二甲缩醛 、 2-bromo-1-ethoxy-2-methyl-1-trimethylsilyoxyethene 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 生成 Ethyl 2-bromo-2-methyl-3-methoxy-3-phenylpropionate
  参考文献：
  名称：

  Stereoselective Hydrogen Transfer Reactions Involving Acyclic Radicals. Tandem Substituted Tetrahydrofuran Formation and Stereoselective Reduction: Synthesis of the C17-C22 Subunit of Ionomycin

  摘要：

  The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.

  DOI：

  10.1021/jo00084a040

文献信息

• The effect of polar substituents on the conformation and stereochemistry of enolate radicals
  作者：B. Giese、W. Damm、F. Wetterich、H.-G. Zeitz、J. Rancourt、Y. Guindon

  DOI：10.1016/s0040-4039(00)73805-6

  日期：1993.9

  ESR measurements and AM1 calculations show that ester substituted radicals 2 and 6 prefer conformation A as a result of allylic strain effects. But dipolar repulsion between substituents X and CO2Et In 2 and 6 has a pronounced effect on the conformation and the stereoselectivity of radicals 2 and 6.

  ESR测量和AM1计算表明，由于烯丙基应变效应，酯取代的基团2和6更偏爱构象A。但是，取代基X和CO 2 Et In 2和6之间的偶极排斥力对自由基2和6的构象和立体选择性具有显着影响。
• Stereoselective Hydrogen Transfer Reactions Involving Acyclic Radicals. Tandem Substituted Tetrahydrofuran Formation and Stereoselective Reduction: Synthesis of the C17-C22 Subunit of Ionomycin
  作者：Y. Guindon、C. Yoakim、V. Gorys、W. W. Ogilvie、D. Delorme、J. Renaud、G. Robinson、J.-F. Lavallee、A. Slassi

  DOI：10.1021/jo00084a040

  日期：1994.3

  The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.