dimethyl 4-(benzoyloxy)-4-phenylhepta-2,5-diynedioate | 945486-19-1

• 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: dimethyl 4-(benzoyloxy)-4-phenylhepta-2,5-diynedioate
• 英文别名: Dimethyl 4-benzoyloxy-4-phenylhepta-2,5-diynedioate
• CAS: 945486-19-1
• 化学式: C₂₂H₁₆O₆
• 分子量: 376.365
• InChiKey: KGMKGWWNCRBVGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 4-(benzoyloxy)-4-phenylhepta-2,5-diynedioate 在 silica gel 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 73.0h， 生成 2-methoxy-1-(6-(2-methoxy-2-oxoethyl)-2-methyl-5-phenylpyrimidin-4-yl)-2-oxoethyl benzoate
  参考文献：
  名称：

  完全取代的嘧啶的合成

  摘要：

  描述了一种新颖的合成全取代嘧啶衍生物的方法，该嘧啶衍生物在环上带有一个氧官能化的乙酸酯链。在偶联的多米诺骨牌策略中，歧管使用am作为氮源，并使用活化的跳过的二炔作为亲电反应性伙伴。在第一个多米诺反应中，两个连续的氮杂-Michael加成反应组装了六元环杂环，而在第二个多米诺反应中，[H]-移位和[3,3]-σ重排导致产物芳构化。

  DOI：

  10.1021/jo400090w
• 作为产物：
  描述：

  苯甲酰氯 、 丙炔酸甲酯 在 三乙胺 作用下， 以70%的产率得到dimethyl 4-(benzoyloxy)-4-phenylhepta-2,5-diynedioate
  参考文献：
  名称：

  Synthesis of γ-Acetoxy β-Keto Esters Through Regioselective Hydration of γ-Acetoxy-α,β-alkynoates

  摘要：

  The At(I)-catalyzed regioselective hydration of gamma-acetoxy-alpha,beta-acetylinic ester by the assistance of a neighboring carbonyl group has beets developed. Varieties of simple primary, secondary, and tertiary gamma-acetoxy-alpha,beta-acetylinic esters, even those bearing sensitive functional group in the remote reaction sites, are selectively hydrated to the corresponding beta-keto esters. The reaction' tolerates a wide variety of other carboxylates, such as benzoates, propionates, acrylates, and pivalates, including chiral carboxylates with retention of the configuration. The broad substrate scope, including the derivatization of complex natural products and neutral and open air conditions, makes this atom economical approach very practical. O-18 labeling experiments disclose that the oxygen transposition occurs from the carboxylate group to the triple bond, not from water.

  DOI：

  10.1021/acs.joc.5b00400

文献信息

• Tertiary Skipped Diynes: A Pluripotent Building Block for the Modular and Diversity-Oriented Synthesis of Nitrogen Heterocycles
  作者：David Tejedor、Sara López-Tosco、Javier González-Platas、Fernando García-Tellado

  DOI：10.1002/chem.200903577

  日期：2010.3.15

  Dominos! The multivalent reactivity profile of tertiary skipped diynes has been conveniently exploited in the domino and diversity‐oriented synthesis of fully substituted pyrazoles and 1,4‐diazepane derivatives (see scheme). The developed manifold is chemically efficient and simple to operate. In addition, the resulting N‐containing heterocycles are obtained in a regio‐ and chemoselective manner.

  多米诺骨牌！在完全取代的吡唑和1,4-二氮杂苯衍生物的多米诺骨牌和面向多样性的合成中，可以方便地利用三级跳过的二炔的多价反应性谱（参见方案）。研发的歧管化学效率高，操作简单。此外，以区域和化学选择性的方式获得了所得的含氮杂环。
• Reactivity Control in the Addition of N,N′-Dialkylated 1,n-Diamines to Activated Skipped Diynes: Synthesis of Fused Bicyclic 1,4-Diazepanes and 1,5-Diazocanes
  作者：Sara López-Tosco、David Tejedor、Javier González-Platas、Fernando García-Tellado

  DOI：10.1002/ejoc.201101368

  日期：2011.12

  This research was supported by the Spanish Spanish Ministerio de Ciencia e Innovacion (MICINN), the European Regional Development Fund (RDF) (CTQ2008-06806-C02-02), and the Spanish Ministerio de Sanidad y Consumo, Instituto de Salud Carlos III (MSC ISCIII) (RETICS RD06/0020/1046) and the Fundacion Canaria de Investigacion y Salud (FUNCIS) (PI 43/09).

  这项研究得到了西班牙西班牙国家科学和创新部长 (MICINN)、欧洲区域发展基金 (RDF) (CTQ2008-06806-C02-02) 和西班牙卫生部长卡洛斯三世 (Instituto de Salud y Consumo) 的支持 ( MSC ISCIII) (RETICS RD06/0020/1046) 和 Fundacion Canaria de Investigacion y Salud (FUNCIS) (PI 43/09)。
• From Conjugated Tertiary Skipped Diynes to Chain-Functionalized Tetrasubstituted Pyrroles
  作者：David Tejedor、Sara López-Tosco、Javier González-Platas、Fernando García-Tellado

  DOI：10.1002/chem.200802262

  日期：2009.1.12

  Privileged scaffolds: Breaking the symmetry of 1,4‐diyne scaffolds by nucleophilic amine addition onto one of two equivalent alkynoate units affords chain‐functionalized tetrasubstituted pyrroles with five points of functional diversity and two points for complexity generation. The domino reaction manifold entails an aza‐Michael addition, a 5‐endo‐digonal cyclization, and a [3,3]‐sigmatropic rearrangement

  特权支架：通过将亲核胺添加到两个等效的炔酸单元之一上来破坏1,4-二炔支架的对称性，可得到链官能化的四取代吡咯，具有五个功能多样性点和两个复杂度生成点。多米诺反应歧管需要进行氮杂-迈克尔加成反应，5-内-数字环化和[3,3]-σ重排。
• Metal-Free Access to Fully Substituted Skipped Diynes. An Efficient Chemodifferentiating A₂BB‘ 4CR Manifold
  作者：David Tejedor、Sara López-Tosco、Javier González-Platas、Fernando García-Tellado

  DOI：10.1021/jo070764y

  日期：2007.7.1

  A metal-free chemodifferentiating A(2)BB' 4CR manifold for the modular synthesis of tertiary skipped diynes is described. The manifold performs a triethylamine triggered reaction of alkyl propiolates and acid chlorides to assemble two units of each component in the form of two propargylic alkynoates, a tertiary alcohol, and an ester. A differentiated incorporation of the two acid chloride components ensures functional diversity in the final structure. In addition, the presence of two connected propargylic alkynoates provides a reactive platform for complexity generation.