methyl (E)-3-(1-methylcyclohexyl)acrylate | 1788861-67-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (E)-3-(1-methylcyclohexyl)acrylate
• 英文别名: 2-Propenoic acid, 3-(1-methylcyclohexyl)-, methyl ester, (2E)-；methyl (E)-3-(1-methylcyclohexyl)prop-2-enoate
• CAS: 1788861-67-5
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: JZINPUSLRGKHGA-RMKNXTFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-甲基环己醇 在 4-二甲氨基吡啶 、 tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate 、 二氢吡啶 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 methyl (E)-3-(1-methylcyclohexyl)acrylate
  参考文献：
  名称：

  利用可见光光催化 N-邻苯二甲酰亚胺酰草酸叔烷基酯生成的叔自由基进行片段偶联和季碳构建。

  摘要：

  叔碳自由基与烯烃受体的偶联是结合复杂碳片段并形成新季碳的尚未开发的策略。描述了从叔醇生成亲核叔自由基并在片段偶联反应中利用这些中间体的新方法的范围和局限性。该方法首先将叔醇酰化，得到N-邻苯二甲酰亚氨基草酸叔烷基酯，在可见光催化下Ru(bpy)3(PF6)2和还原剂片段存在，生成相应的叔醇碳自由基。除了与烯烃的还原偶联外，还描述了叔自由基与烯丙基和乙烯基卤化物的取代反应。基于 Okada 和 Barton 的早期开创性研究，提出了一种由 N-邻苯二甲酰亚氨基草酸叔烷基酯生成叔碳自由基的机制。氘标记和竞争实验表明，N-邻苯二甲酰亚氨基草酸叔烷基酯与缺电子烯烃的还原自由基偶联是通过氢原子转移终止的。

  DOI：

  10.1021/acs.joc.5b00794

文献信息

• Constructing Quaternary Carbons from <i>N</i>-(Acyloxy)phthalimide Precursors of Tertiary Radicals Using Visible-Light Photocatalysis
  作者：Gerald Pratsch、Gregory L. Lackner、Larry E. Overman

  DOI：10.1021/acs.joc.5b00795

  日期：2015.6.19

  Tertiary carbon radicals have notable utility for uniting complex carbon fragments with concomitant formation of new quaternary carbons. This article explores the scope, limitations, and certain mechanistic aspects of Okada's method for forming tertiary carbon radicals from N-(acyloxy)phthalimides by visible-light photocatalysis. Optimized conditions for generating tertiary radicals from N-(acyloxy)phthalimide derivatives of tertiary carboxylic acids by visible-light irradiation in the presence of 1 mol % of commercially available Ru(bpy)(3)(PF6)(2), diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate (8), and i-Pr2NEt and their coupling in dichloromethane at room temperature with alkene acceptors were developed. Four representative tertiary N-(acyloxy)-phthalimides and 15 alkene radical acceptors were examined. Both reductive couplings with electron-deficient alkenes and radical substitution reactions with allylic and vinylic bromides and chlorides were examined with many such reactions occurring in good yield using only a slight excess (typically 1.5 equiv) of the alkene. In general, the yields of these photocatalytic reactions were higher than the analogous transformations of the corresponding N-phthalimidoyl oxalates. Deuterium labeling and competition experiments reveal that the reductive radical coupling of tertiary N-(acyloxy)phthalimides with electron-deficient alkenes can be terminated by both hydrogen-atom transfer and single-electron reduction followed by protonation, and that this mechanistic duality is controlled by the presence or absence of i-Pr2NEt.