Methyl 4-chloro-2-[hydroxy(phenyl)methyl]butanoate | 214424-65-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: Methyl 4-chloro-2-[hydroxy(phenyl)methyl]butanoate
• CAS: 214424-65-4
• 化学式: C₁₂H₁₅ClO₃
• 分子量: 242.702
• InChiKey: ZGUFSIBAFKPHQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 4-chloro-2-[hydroxy(phenyl)methyl]butanoate 在 双[Α,Α-双(三氟甲基)苯甲醇合]二苯硫 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以84%的产率得到methyl (2E)-2-benzylidene-4-chlorobutanoate
  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
• 作为产物：
  描述：

  氯碘甲烷 、 2-(羟基苯基甲基)-丙烯酸甲酯 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 以82%的产率得到Methyl 4-chloro-2-[hydroxy(phenyl)methyl]butanoate
  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

• Diastereoselective Synthesis of Tetrahydrofurans from Aryl 3-Chloropropylsulfoxides and Aldehydes
  作者：Zofia Komsta、Michał Barbasiewicz、Mieczysław Ma̧kosza

  DOI：10.1021/jo1002196

  日期：2010.5.21

  Carbanions of aryl 3-chloropropylsulfoxides react with nonenolizable aldehydes to give 2,3-disubstituted tetrahydrofurans. Deprotonation of the sulfoxides carried out in the presence of aldehydes results in the addition of the carbanions to the carbonyl group of the aldehydes, followed by 1,5-intra-molecular substitution of the resulting aldol-type anion to produce the tetrahydrofuran ring. The 2-aryl and 3-arylsulfinyl substituents are always in trans relation, and the reaction proceeds with high diastereoselectivity also in respect to the chiral sulfur atom. The diastereoselectivity is attributed to the cyclic transition state of the aldol addition and increases when the aromatic ring of the sulfoxide contains electron-withdrawing substituents, whereas that of the aldehyde has eleetron-donatine groups.
• 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.