1-acetyl-2-methylenecyclopentanecarboxylic acid benzyl ester | 1092110-36-5

• 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: 1-acetyl-2-methylenecyclopentanecarboxylic acid benzyl ester
• 英文别名: benzyl 1-acetyl-2-methylenecyclopentanecarboxylate；Benzyl 1-acetyl-2-methylidenecyclopentane-1-carboxylate
• CAS: 1092110-36-5
• 化学式: C₁₆H₁₈O₃
• 分子量: 258.317
• InChiKey: YUNFHDWFBIPZSR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  benzyl 2-acetylhept-6-ynoate 在 silver tetrafluoroborate 、 copper(I) trifluoromethanesulfonate benzene 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 20.0h， 以91%的产率得到1-acetyl-2-methylenecyclopentanecarboxylic acid benzyl ester
  参考文献：
  名称：

  2-烷基1,3-二羰基化合物的铜/银共催化的Conia-Ene反应

  摘要：

  已经开发出铜/银催化的Conia-ene反应，用于选择性地构建五元环和六元环。在（CuOTf）2 ·C 6 H 6和AgBF 4的存在下，各种2-炔基1,3-二羰基化合物顺利进行了Conia-ene分子内反应，产率中等至良好。值得注意的是，在标准条件下，2-苯基乙酰庚基-6腈和2-（戊-4-炔基）丙二酸二乙酯也是合适的底物，对内-或外-产物的选择性取决于末端的取代基。炔烃。

  DOI：

  10.1021/jo802133w

文献信息

• General Zinc-Catalyzed Conia-Ene Reactions of 1,3-Dicarbonyl Compounds with Alkynes Including the Classically Challenging Substrates under Neat Conditions
  作者：Chen-Liang Deng、Ren-Jie Song、Yi-Lin Liu、Jin-Heng Li

  DOI：10.1002/adsc.200900588

  日期：2009.12

  products has been developed by zinc-catalyzed intramolecular Conia-ene reactions of 1,3-dicarbonyl compounds with alkynes. This new route allows a wide range of dicarbonyl compounds, including the classically challenging 1,3-diesters and N,N′-disubstituted 1,3-keto amides, to be used for the Conia-ene reaction with inexpensive zinc chloride (ZnCl2) under neat conditions.

  通过锌催化1,3-二羰基化合物与炔烃的分子内Conia-ene反应，已经开发出一种简单的，多用途的新方法，可将四元环变成六元环。这种新途径允许将广泛的二羰基化合物，包括经典的具有挑战性的1,3-二酯和N，N'-二取代的1,3-酮酰胺，用于与廉价氯化锌（ZnCl 2）。
• Boronic acid catalyzed ene carbocyclization of acetylenic dicarbonyl compounds
  作者：Meiling Li、Ting Yang、Darren J. Dixon

  DOI：10.1039/b924899d

  日期：——

  The discovery and development of an efficient ene carbocyclization of 1,3-dicarbonyl compounds bearing pendent terminal alkyne substituents under 3-nitrobenzeneboronic acid catalysis is described. The reaction is efficient, easy to perform and general to a wide range of ketoester substrates.

  描述了在3-硝基苯硼酸催化下，带有悬垂的末端炔基取代基的1，3-二羰基化合物的有效烯碳环化的发现和发展。该反应是有效的，易于进行的并且通常适用于多种酮酸酯底物。
• Copper/Silver-Cocatalyzed Conia−Ene Reactions of 2-Alkynic 1,3-Dicarbonyl Compounds
  作者：Chen-Liang Deng、Tao Zou、Zhi-Qiang Wang、Ren-Jie Song、Jin-Heng Li

  DOI：10.1021/jo802133w

  日期：2009.1.2

  A copper/silver-catalyzed Conia−ene reaction has been developed for selectively constructing five-membered and six-membered rings. In the presence of (CuOTf)2·C6H6 and AgBF4, a variety of 2-alkynic 1,3-dicarbonyl compounds underwent the Conia−ene intramolecular reaction smoothly in moderate to good yields. It is noteworthy that both 2-phenylacetylhept-6-ynenitrile and diethyl 2-(pent-4-ynyl)malonate

  已经开发出铜/银催化的Conia-ene反应，用于选择性地构建五元环和六元环。在（CuOTf）2 ·C 6 H 6和AgBF 4的存在下，各种2-炔基1,3-二羰基化合物顺利进行了Conia-ene分子内反应，产率中等至良好。值得注意的是，在标准条件下，2-苯基乙酰庚基-6腈和2-（戊-4-炔基）丙二酸二乙酯也是合适的底物，对内-或外-产物的选择性取决于末端的取代基。炔烃。
• An Efficient and General Microwave-Assisted Copper-Catalyzed Conia-Ene Reaction of Terminal and Internal Alkynes Tethered to a Wide Variety of Carbonucleophiles
  作者：Sonia Montel、Didier Bouyssi、Geneviève Balme

  DOI：10.1002/adsc.201000351

  日期：2010.9.10

  This paper describes a highly efficient, microwave‐assisted, Conia‐ene reaction of alkynes bearing a stabilizing carbon nucleophile. The reaction, catalyzed by a commercially available copper catalyst, proceeds under neutral conditions and is generally applicable even to less reactive nucleophiles such as malonate, cyanoacetate, and sulfonylacetate derivatives. This copper‐mediated cycloisomerization

  本文描述了带有稳定碳亲核试剂的炔烃的高效微波辅助的Conia-ene反应。由市售铜催化剂催化的反应在中性条件下进行，并且通常甚至适用于反应性较低的亲核试剂，如丙二酸酯，氰基乙酸酯和磺酰乙酸酯衍生物。这种铜介导的环异构化也适用于内部未活化的炔烃，仅导致相应的具有E烯烃化学性质的五元产物。
• 3,5-Bis(pentafluorosulfanyl)phenylboronic acid: A new organocatalyst for Conia-ene carbocyclization of 1,3-dicarbonyl compounds having terminal alkynes
  作者：Yu-Dong Yang、Xu Lu、Etsuko Tokunaga、Norio Shibata

  DOI：10.1016/j.jfluchem.2012.06.007

  日期：2012.11

  3,5-Bis(pentafluorosulfanyl)phenylboronic acid 1 was introduced as an efficient organocatalyst for Conia-ene carbocyclization of 1,3-dicarbonyl compounds having terminal alkynes. A variety of 2-alkynic 1,3-dicarbonyl compounds were smoothly converted to ene-carbocyclization products in moderate to excellent yields. Compared with the reported catalyst, 3-nitro phenylboronic acid, catalyst 1 is slightly better in a non-polar solvent such as toluene and Solkane(R) 365mfc (1,1,1,3,3-pentafluorobutane). These results indicate that the SF5 function can be a lipophilic and sterically demanding alternative to the NO2 group in catalyst design. (C) 2012 Elsevier B.V. All rights reserved.