3-(2-(ethoxycarbonylethynyl)phenyl)prop-2-ynoic acid ethyl ester | 334868-10-9

• 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: 3-(2-(ethoxycarbonylethynyl)phenyl)prop-2-ynoic acid ethyl ester
• 英文别名: diethyl 3,3'-(1,2-phenylene)dipropiolate；Ethyl 3-[2-(3-ethoxy-3-oxoprop-1-ynyl)phenyl]prop-2-ynoate
• CAS: 334868-10-9
• 化学式: C₁₆H₁₄O₄
• 分子量: 270.285
• InChiKey: SIVXJKQVBZYBJP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  3-(2-(ethoxycarbonylethynyl)phenyl)prop-2-ynoic acid ethyl ester 在 bis(1,5-cyclooctadiene)nickel (0) 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 (-)-1,2-双((2s,5s)-2,5-二甲基膦)乙烷 、 三苯基膦 作用下， 以 四氢呋喃 、 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 9.0h， 生成 (+)-2,7-di-(ethoxycarbonyl)-1,8-diphenyl-9,9,18,18-tetramethyl-9,18-disilaindeno[2,3-c]indeno-[3,2-g]triphenylene
  参考文献：
  名称：

  Highly enantioselective synthesis of silahelicenes using Ir-catalyzed [2+2+2] cycloaddition

  摘要：

  硅螺旋烯是一种包含两个硅烯单元的螺旋手性结构，通过手性铱催化的分子间[2+2+2]环加成反应将四炔与二烯结合合成，同时还进行了镍介导的分子内[2+2+2]环加成反应。所获得的高对映体丰富度的硅螺旋烯（对映体丰度高达93% ee）的光物理性质也进行了测量。

  DOI：

  10.1039/c1cc16762f
• 作为产物：
  描述：

  1,2-bis(2-hydroxy-2-methyl-4-but-3-ynyl)benzene 在 氢氧化钾 、 正丁基锂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， -35.0~160.0 ℃ 、199.98 Pa 条件下， 反应 0.33h， 生成 3-(2-(ethoxycarbonylethynyl)phenyl)prop-2-ynoic acid ethyl ester
  参考文献：
  名称：

  Carbonyl- and Carboxyl-Substituted Enediynes:  Synthesis, Computations, and Thermal Reactivity

  摘要：

  The influence of electron-withdrawing groups (carbonyl and carboxyl) at the alkyne termini on the reactivity of enediynes was investigated by a combination of experimental and computational techniques. While the general chemical reactivity of such enediynes, especially if non-benzannelated, is increased markedly, the thermal cyclization, giving rise to Bergman cyclization products, is changed little relative to the parent enediyne system. This is evident from kinetic measurements and from density functional theory (DFT, BLYP/6-31G* + thermal corrections) computations of the experimental systems which show that the Bergman cyclization barriers slightly (3-4 kcal/mol) increase, in contrast to earlier theoretical predictions. The effect on the endothermicities is large (Delta DeltaH(r) = 7-12 kcal/mol). Hence, the increased reactivity of the substituted enediynes is entirely due to nucleophiles or radicals present in solution. This was demonstrated by quantitative experiments with diethylamine and tetramethyl piperidyl oxide (TEMPO) which both give fulvenes through 5-exo-dig cyclizations.

  DOI：

  10.1021/jo001417q

文献信息

• Aerobic Cu-catalyzed oxidative 1 : 2 coupling of benzynes with terminal alkynes
  作者：Tianhao Lu、Yong Shen、Min Wang、Zibing Zhang、Shijun Li、Chunsong Xie

  DOI：10.1039/d0cc03150j

  日期：——

  Cu-Catalyzed oxidative 1 : 2 couplings of arynes with nucleophilic terminal alkynes under aerobic conditions are described herein. A mechanistic investigation revealed a plausible involvement of an aryl-Cu(III)-generating pathway. By this method, ubiquitous arenediynes can be efficiently assembled in a single step under mild conditions.

  本文描述了在有氧条件下，芳烃与亲核末端炔烃的Cu催化的氧化1：2偶联。一项机械调查显示，可能发生了芳基-铜（III）生成途径。通过这种方法，可以在温和的条件下一步完成无处不在的芳烃。
• Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
  作者：Flemming Heinen、Elric Engelage、Christopher J. Cramer、Stefan M. Huber

  DOI：10.1021/jacs.9b13309

  日期：2020.5.13

  “Hypervalent” iodine(III) derivatives have been established as powerful reagents in organic transformations, but so far only a handful of studies have addressed their potential use as halogen-bonding noncovalent Lewis acids. In contrast to “classical” halogen-bond donors based on iodine(I) compounds, iodine(III) salts feature two directional electrophilic axes perpendicular to each other. Herein we

  “超价”碘 (III) 衍生物已被确定为有机转化中的强大试剂，但到目前为止，只有少数研究解决了它们作为卤素键合非共价路易斯酸的潜在用途。与基于碘 (I) 化合物的“经典”卤素键供体相比，碘 (III) 盐具有两个相互垂直的定向亲电轴。在此，我们首次对溶液中与此类路易斯酸的双轴结合进行了系统研究。为此，通过 1 H NMR 光谱和等温滴定量热法，用各种底物（包括二酯和二酰胺）滴定受阻和不受阻碍的碘化物。在两个模型系统中获得了双轴结合的明确证据，关联强度增加了 2 个数量级。
• Highly enantioselective synthesis of silahelicenes using Ir-catalyzed [2+2+2] cycloaddition
  作者：Takanori Shibata、Toshifumi Uchiyama、Yusuke Yoshinami、Satoshi Takayasu、Kyoji Tsuchikama、Kohei Endo

  DOI：10.1039/c1cc16762f

  日期：——

  Silahelicenes, which contain two silole moieties in a helically chiral structure, were synthesized by a chiral Ir-catalyzed intermolecular [2+2+2] cycloaddition of tetraynes with diynes along with a Ni-mediated intramolecular [2+2+2] cycloaddition. The photophysical properties of the obtained highly enantiomerically enriched silahelicenes (up to 93% ee) were also measured.

  硅螺旋烯是一种包含两个硅烯单元的螺旋手性结构，通过手性铱催化的分子间[2+2+2]环加成反应将四炔与二烯结合合成，同时还进行了镍介导的分子内[2+2+2]环加成反应。所获得的高对映体丰富度的硅螺旋烯（对映体丰度高达93% ee）的光物理性质也进行了测量。
• Carbonyl- and Carboxyl-Substituted Enediynes:  Synthesis, Computations, and Thermal Reactivity
  作者：Burkhard König、Wolfgang Pitsch、Michael Klein、Rudolf Vasold、Matthias Prall、Peter R. Schreiner

  DOI：10.1021/jo001417q

  日期：2001.3.1

  The influence of electron-withdrawing groups (carbonyl and carboxyl) at the alkyne termini on the reactivity of enediynes was investigated by a combination of experimental and computational techniques. While the general chemical reactivity of such enediynes, especially if non-benzannelated, is increased markedly, the thermal cyclization, giving rise to Bergman cyclization products, is changed little relative to the parent enediyne system. This is evident from kinetic measurements and from density functional theory (DFT, BLYP/6-31G* + thermal corrections) computations of the experimental systems which show that the Bergman cyclization barriers slightly (3-4 kcal/mol) increase, in contrast to earlier theoretical predictions. The effect on the endothermicities is large (Delta DeltaH(r) = 7-12 kcal/mol). Hence, the increased reactivity of the substituted enediynes is entirely due to nucleophiles or radicals present in solution. This was demonstrated by quantitative experiments with diethylamine and tetramethyl piperidyl oxide (TEMPO) which both give fulvenes through 5-exo-dig cyclizations.