methyl (2S,3S)-2-bromo-3-methoxy-2-methyl-3-phenylpropanoate | 141320-38-9

• 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: methyl (2S,3S)-2-bromo-3-methoxy-2-methyl-3-phenylpropanoate
• CAS: 141320-38-9
• 化学式: C₁₂H₁₅BrO₃
• 分子量: 287.153
• InChiKey: FCFJRRMXKDWJOW-JQWIXIFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  methyl (2S,3S)-2-bromo-3-methoxy-2-methyl-3-phenylpropanoate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以86%的产率得到syn methyl 3-methoxy-2-methyl-3-phenylpropanoate
  参考文献：
  名称：

  Stereoselective hydrogen-transfer reactions involving acyclic radicals. A study of radical conformations using semiempirical calculations

  摘要：

  DOI：

  10.1021/ja00038a072
• 作为产物：
  描述：

  甲醇 、 (E)-methyl-2-methyl-3-phenylacrylate 在 溴 、 silver nitrate 作用下， 反应 1.0h， 以93%的产率得到methyl (2S,3S)-2-bromo-3-methoxy-2-methyl-3-phenylpropanoate
  参考文献：
  名称：

  The Use of Lewis Acids in Radical Chemistry. Chelation-Controlled Radical Reductions of Substituted α-Bromo-β-alkoxy Esters and Chelation-Controlled Radical Addition Reactions

  摘要：

  The radical reduction of a series of alpha-bromo-beta-alkoxy esters under chelation-controlled conditions is reported. Proceeding with high stereoselectivity in the presence of MgBr2. OEt2, reductions give access to syn, products. Systematic variations in substrate substituents show that these reactions tolerate a wide variety of alkyl functionalities at positions 2 and 3 and are relatively unaffected by the nature of the ester group. Changes to the alkoxy function indicate that a bidentate chelate is involved in the reaction and that an excess of MgBr2. OEt2 is required for optimum selectivity by favoring this species in preference to the anti-selective monodentate or nonchelated pathways. Competition experiments suggest that the monodentate pathway is kinetically favored over the bidentate one. The suppressibility of the reaction by radical chain inhibitors and the need for initiation indicate the intermediacy of radicals. Further support for this mechanism includes both radical addition to alpha,beta-unsaturated esters and reduction of bromides conducted in the presence of a Lewis acid.

  DOI：

  10.1021/jo980636x

文献信息

• The Use of Lewis Acids in Radical Chemistry. Chelation-Controlled Radical Reductions of Substituted α-Bromo-β-alkoxy Esters and Chelation-Controlled Radical Addition Reactions
  作者：Yvan Guindon、J. Rancourt

  DOI：10.1021/jo980636x

  日期：1998.9.1

  The radical reduction of a series of alpha-bromo-beta-alkoxy esters under chelation-controlled conditions is reported. Proceeding with high stereoselectivity in the presence of MgBr2. OEt2, reductions give access to syn, products. Systematic variations in substrate substituents show that these reactions tolerate a wide variety of alkyl functionalities at positions 2 and 3 and are relatively unaffected by the nature of the ester group. Changes to the alkoxy function indicate that a bidentate chelate is involved in the reaction and that an excess of MgBr2. OEt2 is required for optimum selectivity by favoring this species in preference to the anti-selective monodentate or nonchelated pathways. Competition experiments suggest that the monodentate pathway is kinetically favored over the bidentate one. The suppressibility of the reaction by radical chain inhibitors and the need for initiation indicate the intermediacy of radicals. Further support for this mechanism includes both radical addition to alpha,beta-unsaturated esters and reduction of bromides conducted in the presence of a Lewis acid.
• Stereoselective hydrogen-transfer reactions involving acyclic radicals. A study of radical conformations using semiempirical calculations
  作者：K. Durkin、D. Liotta、J. Rancourt、J. F. Lavallee、L. Boisvert、Y. Guindon

  DOI：10.1021/ja00038a072

  日期：1992.6