diethyl 2-benzyl-2-(but-2-yn-1-yl)malonate

• 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: diethyl 2-benzyl-2-(but-2-yn-1-yl)malonate
• 英文别名: ethyl 2-benzyl-2-carboethoxyhex-4-ynoate；Ethyl 2-benzyl-2-carboethoxy-4-hexynoate；diethyl 2-benzyl-2-but-2-ynylpropanedioate
• 化学式: C₁₈H₂₂O₄
• 分子量: 302.37
• InChiKey: BDUBXEARHPYDQE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2-benzyl-2-(but-2-yn-1-yl)malonate 在 喹啉 、 氢气 作用下， 以 甲苯 为溶剂， 反应 0.34h， 以86%的产率得到(Z)-diethyl 2-benzyl-2-(but-2-en-1-yl)malonate
  参考文献：
  名称：

  Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors

  摘要：

  The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.

  DOI：

  10.1021/ja4050168
• 作为产物：
  描述：

  二苄基丙二酸二乙酯 在 N,N,N',N'-tetramethyl-7,8-dihydro-6H-dipyrido[1,2-a;2',1'-c][1,4]diazepine-2,12-diamine 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 88.5h， 生成 diethyl 2-benzyl-2-(but-2-yn-1-yl)malonate
  参考文献：
  名称：

  Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors

  摘要：

  The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.

  DOI：

  10.1021/ja4050168

文献信息

• Ynenolactone protease inhibitors
  申请人：Syntex (U.S.A.) Inc.

  公开号：US04602006A1

  公开（公告）日：1986-07-22

  Compounds of the formula ##STR1## wherein n is 1-3; R.sup.1, R.sup.2 and R.sup.3 are the same or different and are hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl or aryl lower alkyl wherein when aryl is phenyl it is unsubstituted or independently substituted with one or more halo, lower alkyl or lower alkoxy groups; and R.sup.4 is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, trialkylsilyl, aryl or aryl lower alkyl wherein when aryl is phenyl it is unsubstituted or independently substituted by one or more halo, lower alkyl or lower alkoxy groups; excluding those compounds wherein R.sup.1 and R.sup.2 are hydrogen and R.sup.4 is ethyl, propyl or butyl. These compounds are useful as protease inhibitors.

  化合物的公式为##STR1## 其中n为1-3；R.sup.1，R.sup.2和R.sup.3相同或不同，可以是氢，低烷基，低烯基，低炔基，芳基或芳基低烷基，其中当芳基为苯基时，它是未取代的或独立取代的，取代基可以是一个或多个卤素，低烷基或低烷氧基；R.sup.4是氢，低烷基，低烯基，低炔基，三烷基硅基，芳基或芳基低烷基，其中当芳基为苯基时，它是未取代的或独立取代的，取代基可以是一个或多个卤素，低烷基或低烷氧基；不包括R.sup.1和R.sup.2为氢，R.sup.4为乙基，丙基或丁基的化合物。这些化合物可用作蛋白酶抑制剂。
• US4602006A
  申请人：——

  公开号：US4602006A

  公开（公告）日：1986-07-22
• Overturning Established Chemoselectivities: Selective Reduction of Arenes over Malonates and Cyanoacetates by Photoactivated Organic Electron Donors
  作者：Eswararao Doni、Bhaskar Mondal、Steven O’Sullivan、Tell Tuttle、John A. Murphy

  DOI：10.1021/ja4050168

  日期：2013.7.31

  The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.