1,1a,6,6a-Tetrahydrocyclopropinden-6-on | 42916-16-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 1,1a,6,6a-Tetrahydrocyclopropinden-6-on
• 英文别名: 1a,6a-Dihydrocyclopropa[a]inden-6(1H)-one；1a,6a-dihydro-1H-cyclopropa[a]inden-6-one
• CAS: 42916-16-5
• 化学式: C₁₀H₈O
• mdl: MFCD02258683
• 分子量: 144.173
• InChiKey: MYLRFVFSHGOPFU-UHFFFAOYSA-N

物化性质

• 沸点：
  242.9±10.0 °C(Predicted)
• 密度：
  1.267±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

上下游信息

反应信息

• 作为反应物：
  描述：

  1,1a,6,6a-Tetrahydrocyclopropinden-6-on 在 吡啶 、 aluminum isopropoxide 作用下， 以 异丙醇 为溶剂， 生成 1,1a,6,6a-tetrahydrocyclopropa[a]inden-6-yl 3,5-dinitrobenzoate
  参考文献：
  名称：

  Cyclopropylcarbinyl cation chemistry and antihomoaromaticity in the cycloprop[2,3]inden-1-yl cation system

  摘要：

  DOI：

  10.1021/jo00428a037
• 作为产物：
  描述：

  2-苯基环丙烷羰酰氯 生成 1,1a,6,6a-Tetrahydrocyclopropinden-6-on
  参考文献：
  名称：

  Stable carbocations. CLXXXVIII. Bicyclo[3.1.0]hexenyl cations

  摘要：

  DOI：

  10.1021/jo00910a021

文献信息

• The friedel-crafts reaction of acid chlorides with ethene ; Di-addition and molecular rearrangement
  作者：Francis X Bates、John A Donnelly、John R Keegan

  DOI：10.1016/s0040-4020(01)80962-5

  日期：1991.1

  Acid chlorides, complexed with excess aluminium chloride, reacted with ethene to form 3-methyl-2-buten-1-ones, i.e. rearranged di-addition products having a terminal isoprenoid skeleton, together with the usual β-chloropropanones. The latter were the sole products in the absence of excess catalyst. Acid chlorides containing a suitably situated π-system underwent intramolecular cyclization, e.g. 2-

  酰氯与过量的氯化铝络合，与乙烯反应形成3-甲基-2-丁烯-1-酮，即具有末端类异戊二烯骨架的重排二加成产物，以及通常的β-氯丙烷。后者是在没有过量催化剂的情况下的唯一产物。含有适当位置的π系统的酰氯进行了分子内环化，例如将2-苯基环丙烷羰基氯（10）环化为3,4-苯并双环[3.1.0]己-2-酮（11）。
• Metal-Free Synthesis of C-4 Substituted Pyridine Derivatives Using Pyridine-boryl Radicals via a Radical Addition/Coupling Mechanism: A Combined Computational and Experimental Study
  作者：Guoqiang Wang、Jia Cao、Liuzhou Gao、Wenxin Chen、Wenhao Huang、Xu Cheng、Shuhua Li

  DOI：10.1021/jacs.7b00823

  日期：2017.3.15

  that the pyridine-boryl radical generated in situ using 4-cyanopyridine and bis(pinacolato)diboron could be used as a bifunctional "reagent", which serves as not only a pyridine precursor but also a boryl radical. With the unique reactivity of such radicals, 4-substituted pyridine derivatives could be synthesized using α,β-unsaturated ketones and 4-cyanopyridine via a novel radical addition/C-C coupling

  密度泛函理论研究表明，使用 4-氰基吡啶和双（频哪醇）二硼原位生成的吡啶-硼基自由基可用作双功能“试剂”，其不仅可用作吡啶前体，还可用作硼基自由基。由于这些自由基的独特反应性，可以使用α,β-不饱和酮和4-氰基吡啶通过新型自由基加成/CC偶联机制合成4-取代吡啶衍生物。进行了几个对照实验，为所提出的机制提供支持性证据。除了烯酮，范围还可以扩展到广泛的硼基自由基受体，包括各种醛和酮、芳基亚胺和炔酮。最后，这种转化应用于复杂药物分子的后期修饰。
• Superacid-Catalyzed Reactions of Cinnamic Acids and the Role of Superelectrophiles¹
  作者：Rendy、Yun Zhang、Aaron McElrea、Alma Gomez、Douglas A. Klumpp

  DOI：10.1021/jo030327t

  日期：2004.4.1

  formation of dicationic intermediates (superelectrophiles), and the reactions can lead to either chalcone-type products or indanone products. The direct observation of a dicationic species (by low-temperature 13C NMR) is reported. We provide clear evidence that protonated carboxylic acid groups (or the corresponding acyl cation) can enhance the reactivity of an adjacent electrophilic center. Triflic acid

  已经研究了肉桂酸和相关化合物的化学性质。在超酸催化的芳烃反应中，提出了两种相互竞争的反应机理。两种机理都涉及形成阳离子型中间体（超亲电子试剂），并且这些反应可导致查尔酮类产物或茚满酮产物。据报道直接观察到一种特殊的物质（通过低温13 C NMR）。我们提供了明确的证据，表明质子化的羧酸基团（或相应的酰基阳离子）可以增强相邻亲电中心的反应活性。三氟甲磺酸还被发现是从肉桂酸直接合成某些缺电子的查耳酮和杂环查耳酮的有效酸催化剂。
• Selective [2σ + 2σ] Cycloaddition Enabled by Boronyl Radical Catalysis: Synthesis of Highly Substituted Bicyclo[3.1.1]heptanes
  作者：Tao Yu、Jinbo Yang、Zhijun Wang、Zhengwei Ding、Ming Xu、Jingru Wen、Liang Xu、Pengfei Li

  DOI：10.1021/jacs.2c13740

  日期：——

  2σ] radical cycloaddition between bicyclo[1.1.0]butanes (BCBs) and cyclopropyl ketones has been developed to provide a modular, concise, and atom-economical synthetic route to substituted bicyclo[3.1.1]heptane (BCH) derivatives that are 3D bioisosteres of benzenes and core skeleton of a number of terpene natural products. The reaction was catalyzed by a combination of simple tetraalkoxydiboron(4) compound

  与传统且广泛使用的至少涉及 π 键组分的环加成反应相比，双环[1.1.0]丁烷 (BCB) 和环丙基酮之间的 [2σ + 2σ] 自由基环加成反应已被开发出来，以提供模块化、简洁的方法。 ，以及取代双环[3.1.1]庚烷（BCH）衍生物的原子经济合成路线，该衍生物是苯的3D生物等排体和许多萜烯天然产物的核心骨架。该反应由简单的四烷氧基二硼(4)化合物B 2 pin 2和异烟酸3-戊酯的组合催化。通过合成一系列新型高度功能化的 BCH，其核心上具有多达 6 个取代基，分离产率高达 99%，证明了其广泛的底物范围。计算机理研究支持吡啶辅助的硼基自由基催化循环。
• A comparative study of the decomposition of o-alkynyl-substituted aryl diazo ketones. Synthesis of polysubstituted .beta.-naphthols via arylketene intermediates
  作者：Albert Padwa、Ugo Chiacchio、David J. Fairfax、Jamal M. Kassir、Angelo Litrico、Mark A. Semones、Simon L. Xu

  DOI：10.1021/jo00075a045

  日期：1993.11

  The photochemical, thermal, and rhodium-catalyzed decomposition reactions of several closely related o-alkynyl or o-alkenyl alpha-diazoaceto- and propiophenone derivatives have been studied. The reaction outcome is markedly dependent upon the reaction conditions employed for nitrogen extrusion. Thermolysis or photolysis of o-alkynyl alpha-diazopropiophenone derivatives yields polysubstituted beta-naphthols. These products are derived from Wolff rearrangement of the initially formed carbene to give an aryl ketene which undergoes intramolecular cyclization onto the o-alkynyl substituent. In direct contrast to the thermal and photochemical results, Rh(II)-catalyzed decomposition yields products derived from direct attack of a rhodium carbenoid onto the tethered pi-system producing a vinyl carbenoid intermediate. Further reaction of the cyclized carbenoid with the starting diazo compound furnishes a vinyl indenone which undergoes a rapid intramolecular Diels-Alder reaction to produce a novel dimer whose structure was elucidated by an X-ray crystal analysis. Replacement of the methyl group on the diazo center with a sterically less demanding hydrogen atom was also found to play an important role in controlling the outcome of the Rh(II)-catalyzed reaction.