1-acetyl-1-methoxycarbonyl-2-methylene cyclohexane | 134149-23-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 1-acetyl-1-methoxycarbonyl-2-methylene cyclohexane
• 英文别名: methyl 1-acetyl-2-methylcyclohexane-2-enecarboxylate；Methyl 1-acetyl-2-methylidenecyclohexane-1-carboxylate
• CAS: 134149-23-8
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: YWAUOTUPFLCJDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  甲磺酸己-5-炔基酯 在 18-冠醚-6 、 Pd(dppe) 、 potassium tert-butylate 作用下， 反应 30.17h， 生成 1-acetyl-1-methoxycarbonyl-2-methylene cyclohexane
  参考文献：
  名称：

  Formation de derives cyclopentaniques assistee par une espece hydrure de palladium : Aspects synthetiques et mecanisme

  摘要：

  In the presence of a palladium(0) complex and potassium t-butoxide, the acetylenic compounds 2 bearing in delta a nucleophilic functionality are smoothly transformed with excellent yields, either into 2,2-difunctionalized methylene cyclopentanes or into monofunctionalized 2-methylcyclopentenes. Each of these compounds can be specifically obtained depending on the choice of the experimental conditions.A set of diverse reactions involving mainly potassium hydride as the base showed clearly that HPdOtBu is not the active catalytic species which is mainly a sigma-ethynylpalladium hydride formed by the metal insertion in the acetylenic carbon hydrogen bond.

  DOI：

  10.1016/s0040-4020(01)89040-2

文献信息

• Introverted Phosphorus-Au Cavitands for Catalytic Use
  作者：Michael P. Schramm、Mao Kanaura、Kouhei Ito、Masataka Ide、Tetsuo Iwasawa

  DOI：10.1002/ejoc.201501426

  日期：2016.2

  an inwardly directed phosphoramidite-Au complex is described and a description of some of its catalytic performance. The molecular structure was determined by crystallographic analysis, which disclosed that the phosphoramidite ligand points “out” and places the complexed Au “in”. We investigated its catalytic activities and found that the inwardly directed Au is surrounded by three inert walls that provide

  描述了一种内向亚磷酰胺-Au 复合物的制备合成及其一些催化性能的描述。分子结构是通过晶体学分析确定的，这表明亚磷酰胺配体指向“外”并将络合的金置于“内”。我们研究了它的催化活性，发现向内定向的 Au 被三个惰性壁包围，这为超分子催化和反应中间体的研究提供了新的机会。
• Using Triethynylphosphine Ligands Bearing Bulky End Caps To Create a Holey Catalytic Environment:  Application to Gold(I)-Catalyzed Alkyne Cyclizations
  作者：Atsuko Ochida、Hideto Ito、Masaya Sawamura

  DOI：10.1021/ja066800c

  日期：2006.12.1

  and catalytic uses of phosphinoalkynes bearing bulky end caps at the alkyne termini, that is, tris[(triarylsilyl)ethynyl]phosphines are reported. The most salient feature of the new phosphines is the holey molecular shape possessing a deep and large-scale metal-binding cavity. The holey phosphines displayed remarkable rate enhancement in the gold(I)-catalyzed six- and seven-membered ring forming cyclizations

  报道了在炔末端带有庞大端盖的膦炔烃的合成、性质和催化用途，即三[（三芳基甲硅烷基）乙炔基]膦。新型膦最显着的特征是具有深而大尺度金属结合腔的多孔分子形状。多孔膦在金（I）催化的乙炔酮酯和 1,7-烯炔的六元和七元环形成环化中显示出显着的速率增强。有人提出，配体中的空腔迫使炔属化合物的亲核中心（烯醇或烯烃）靠近与金结合的炔烃，从而使闭环抗攻击成为可能。
• 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）。
• Metal–ligand–Lewis acid multi-cooperative catalysis: a step forward in the Conia-ene reaction
  作者：Arnaud Clerc、Enrico Marelli、Nicolas Adet、Julien Monot、Blanca Martín-Vaca、Didier Bourissou

  DOI：10.1039/d0sc05036a

  日期：——

  An original multi-cooperative catalytic approach was developed by combining metal–ligand cooperation and Lewis acid activation. The [(SCS)Pd]2 complex featuring a non-innocent indenediide-based ligand was found to be a very efficient and versatile catalyst for the Conia-ene reaction, when associated with Mg(OTf)2. The reaction operates at low catalytic loadings under mild conditions with HFIP as a

  通过结合金属-配体配合和路易斯酸活化作用，开发了一种原始的多配合催化方法。当与Mg（OTf）2缔合时，发现具有非纯茚基二配体的[（SCS）Pd] 2络合物是一种非常有效和通用的柯尼烯反应催化剂。以HFIP为助溶剂，该反应在温和条件下以低催化负载量进行。它适用于多种基质，包括带有内部炔烃的基质。它显示了完整的5- exo与6 - endo区域选择性。此外，除了高度拥塞的t Bu取代基外，Z与E的反应较高 立体选择性，使其在合成上有用并与已知催化剂互补。
• Cyclisation of ω-unsaturated β-dicarbonylcompounds catalyzed by a palladium hydride species
  作者：Nuno Monteiro、Geneviève Balme、Jacques Gore

  DOI：10.1016/s0040-4039(00)74294-8

  日期：1991.3

  When treated with potassium t-butoxide and then with a palladium(O) complex, the title compounds 1, 2, or 9 are smoothly cyclized by an attack of the enolates onto the unsaturation assisted by a palladium (II) species of tBuO-Pd-H type. The formation of a five-membered ring is particularly favored in such a process.