(S)-ethyl 2-hydroxy-4-p-tolylpent-4-enoate

• 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: (S)-ethyl 2-hydroxy-4-p-tolylpent-4-enoate
• 英文别名: ethyl (S)-2-hydroxy-4-p-tolylpent-4-enoate；ethyl (2S)-2-hydroxy-4-(4-methylphenyl)pent-4-enoate
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: RJRIACWKFLXMIF-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  (S)-ethyl 2-hydroxy-4-p-tolylpent-4-enoate 、 丙醛 在 iron(III) chloride 、 叔丁基二甲基氯硅烷 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  Completely OH-Selective FeCl₃-Catalyzed Prins Cyclization: Highly Stereoselective Synthesis of 4-OH-Tetrahydropyrans

  摘要：

  The completely OH-selective Prins cyclization has been realized from the enantioselective ene reaction product. A variety of 4-hydroxyl-tetrahydropyrans were exclusively generated via FeCl3-catalyzed Prins reaction. Excellent stereoselectivities (up to >99:1 dr and >99.5:0.5 er) were obtained for a remarkably broad range of substrates under mild reaction conditions. The control experiments, including NOE effects and O-18-labeling studies, as well as DFT calculations were conducted to provide fundamental insights into the mechanism of the reaction. A different [2 + 2] cycloaddition process was suggested to rationalize the observed OH-selectivity.

  DOI：

  10.1021/ja3062002
• 作为产物：
  描述：

  乙醛酸乙酯 、 1-甲基-4-(1-甲基乙烯基)苯 在 2,6-二叔丁基吡啶 、 [Rh₂(S,S-MenPY)₄]SbF₆ 作用下， 以 neat (no solvent) 为溶剂， 反应 72.0h， 以94%的产率得到(S)-ethyl 2-hydroxy-4-p-tolylpent-4-enoate
  参考文献：
  名称：

  手性阳离子氨基甲酸吡啶二酯（II，III）催化对映选择性羰基-烯反应

  摘要：

  本文描述了乙醛酸酯与手性阳离子氨基羧酸二氨基（II，III）催化的乙醛酸酯与1,1-二取代烯烃的对映选择性羰基-烯反应。在每个铑上具有一个开放配位位的氨基甲酸二（II，III）氨基甲酸酯能平稳地催化羰基-烯反应，以高分离度和良好的对映选择性提供均相醇产物。

  DOI：

  10.1021/jo5013674

文献信息

• Significant counterion effect of the In(III)–pybox complex in highly enantioselective carbonyl-ene reactions of ethyl glyoxylate
  作者：Jun-Feng Zhao、Teguh-Budiono W. Tjan、Teck-Peng Loh

  DOI：10.1016/j.tetlet.2010.06.066

  日期：2010.10

  A highly efficient enantioselective carbonyl-ene reaction of ethyl glyoxylate catalyzed by an In(III)-pybox complex, which is designed based on the counterion effect, is reported. Reactions of both aliphatic and aromatic 1,1-disubstituted olefins proceed smoothly to give enantioenriched homoallylic alcohols with excellent yields and enantioselectivities. In addition, electron-withdrawing as well as donating groups on the phenyl ring of alpha-methyl styrenes are tolerated in this reaction. (C) 2010 Elsevier Ltd. All rights reserved.
• Enantioselective Carbonyl–Ene Reactions Catalyzed by Chiral Cationic Dirhodium(II,III) Carboxamidates
  作者：Xichen Xu、Xiaochen Wang、Yuxiao Liu、Michael P. Doyle

  DOI：10.1021/jo5013674

  日期：2014.12.19

  An enantioselective carbonyl–ene reaction of glyoxylate esters with 1,1-disubstituted alkenes catalyzed by chiral cationic dirhodium(II,III) carboxamidates is described. The paddlewheel dirhodium(II,III) carboxamidates having one open coordination site at each rhodium smoothly catalyze the carbonyl–ene reaction to afford homoallylic alcohol products in good isolated yields with high enantioselectivities

  本文描述了乙醛酸酯与手性阳离子氨基羧酸二氨基（II，III）催化的乙醛酸酯与1,1-二取代烯烃的对映选择性羰基-烯反应。在每个铑上具有一个开放配位位的氨基甲酸二（II，III）氨基甲酸酯能平稳地催化羰基-烯反应，以高分离度和良好的对映选择性提供均相醇产物。
• Completely OH-Selective FeCl₃-Catalyzed Prins Cyclization: Highly Stereoselective Synthesis of 4-OH-Tetrahydropyrans
  作者：Ke Zheng、Xiaohua Liu、Song Qin、Mingsheng Xie、Lili Lin、Changwei Hu、Xiaoming Feng

  DOI：10.1021/ja3062002

  日期：2012.10.24

  The completely OH-selective Prins cyclization has been realized from the enantioselective ene reaction product. A variety of 4-hydroxyl-tetrahydropyrans were exclusively generated via FeCl3-catalyzed Prins reaction. Excellent stereoselectivities (up to >99:1 dr and >99.5:0.5 er) were obtained for a remarkably broad range of substrates under mild reaction conditions. The control experiments, including NOE effects and O-18-labeling studies, as well as DFT calculations were conducted to provide fundamental insights into the mechanism of the reaction. A different [2 + 2] cycloaddition process was suggested to rationalize the observed OH-selectivity.