3-Oxo-butyric acid (1R,3S)-1-methyl-3-o-tolyloxy-butyl ester | 322478-56-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-Oxo-butyric acid (1R,3S)-1-methyl-3-o-tolyloxy-butyl ester
• CAS: 322478-56-8
• 化学式: C₁₆H₂₂O₄
• 分子量: 278.348
• InChiKey: JYMXQOGYIPMBOX-UONOGXRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  20.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  3-Oxo-butyric acid (1R,3S)-1-methyl-3-o-tolyloxy-butyl ester 在 dirhodium tetraacetate 对甲苯磺酰叠氮 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 (3S,5R,8S)-3,5,11-Trimethyl-2,6-dioxa-bicyclo[6.3.2]trideca-1(11),9,12-trien-7-one
  参考文献：
  名称：

  Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions

  摘要：

  [GRAPHICS]Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term, The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.

  DOI：

  10.1021/ol006741m
• 作为产物：
  描述：

  邻甲酚 在 偶氮二甲酸二异丙酯 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 96.0h， 生成 3-Oxo-butyric acid (1R,3S)-1-methyl-3-o-tolyloxy-butyl ester
  参考文献：
  名称：

  Remote stereocontrol of intramolecular rhodium carbene addition driven by a small and flexible chiral 2,4-pentanediol tether

  摘要：

  Intramolecular rhodium carbenoid additions were studied using 2,4-pentanidiol as a chiral tether between a diazo group, a precursor of the carbene, and an aromatic group to be reacted with the carbene. The reaction was designed to perform the addition at a remote position, conserving the original high stereoselectivity appeared at additions near the tether, in addition to high regioselectivity and sufficient reaction efficiency. Substitution on the near reaction sites, the carbene carbon and aromatic group, in the reactant was effective to relegate the reaction site to a remote position. In the present study, two remote reactions, one dealing with C-H insertion and the other classified in Buchner reaction, were found to give sole products in high yields. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.009