rel-(2R,3R)-methyl 2-deuterio-3-methoxy-3-phenylpropanoate | 141320-45-8

• 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: rel-(2R,3R)-methyl 2-deuterio-3-methoxy-3-phenylpropanoate
• 英文别名: methyl (2R,3R)-2-deuterio-3-methoxy-3-phenylpropanoate
• CAS: 141320-45-8；141320-46-9
• 化学式: C₁₁H₁₄O₃
• 分子量: 195.222
• InChiKey: KGPCYWGHIZJCBO-FSBOJYMCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl 2-bromo-3-hydroxy-3-phenylpropanoate 在 偶氮二异丁腈 、 1,8-双二甲氨基萘 、 氘代三正丁基锡 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 rel-(2R,3R)-methyl 2-deuterio-3-methoxy-3-phenylpropanoate
  参考文献：
  名称：

  Investigation of a model for 1,2-asymmetric induction in reactions of .alpha.-carbalkoxy radicals: a stereochemical comparison of reactions of .alpha.-carbalkoxy radicals and ester enolates

  摘要：

  The stereochemical course of reductions and allylations of alpha-carbalkoxy radicals with chiral centers at the beta-position are reported. Radicals without polar substituents, with alkoxyl or acetoxyl groups, and with hydroxyl groups at the beta-position were examined. Reactions showed selectivities ranging from low (50:50) to high (99:1). The results are discussed in terms of transition-state models that emphasize the importance of (1) allylic conformational analysis (minimization of A1,3 and A1,2 strain), (2) torisonal strain (minimization of eclipsed interactions), and (3) stereoelectronic effects.

  DOI：

  10.1021/jo00042a029

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.
• Investigation of a model for 1,2-asymmetric induction in reactions of .alpha.-carbalkoxy radicals: a stereochemical comparison of reactions of .alpha.-carbalkoxy radicals and ester enolates
  作者：David J. Hart、Ramanarayanan Krishnamurthy

  DOI：10.1021/jo00042a029

  日期：1992.7

  The stereochemical course of reductions and allylations of alpha-carbalkoxy radicals with chiral centers at the beta-position are reported. Radicals without polar substituents, with alkoxyl or acetoxyl groups, and with hydroxyl groups at the beta-position were examined. Reactions showed selectivities ranging from low (50:50) to high (99:1). The results are discussed in terms of transition-state models that emphasize the importance of (1) allylic conformational analysis (minimization of A1,3 and A1,2 strain), (2) torisonal strain (minimization of eclipsed interactions), and (3) stereoelectronic effects.