(S)-3-((R)-Methoxy-phenyl-methyl)-4-methylene-cyclopentane-1,1-dicarboxylic acid dimethyl ester

• 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: (S)-3-((R)-Methoxy-phenyl-methyl)-4-methylene-cyclopentane-1,1-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl (3S)-3-[(R)-methoxy(phenyl)methyl]-4-methylidenecyclopentane-1,1-dicarboxylate
• 化学式: C₁₈H₂₂O₅
• 分子量: 318.37
• InChiKey: ZVNYWKOEOLVCEA-GJZGRUSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  dimethyl (E)-2-(prop-2-yn-1-yl)-2-styrylmalonate 在 [Au(Cl₂)((R)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole)]⁺BF₄^- 作用下， 以 甲醇 、 氘代乙腈 为溶剂， 反应 24.0h， 生成 (S)-3-((R)-Methoxy-phenyl-methyl)-4-methylene-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Mechanism of Au(III)-Mediated Alkoxycyclization of a 1,6-Enyne

  摘要：

  Gold-mediated homogeneous catalysis is a powerful tool for construction of valuable molecules and has lately received growing attention. Whereas Au(I)-catalyzed processes have become well established, those mediated by Au(III) have so far barely been explored, and their mechanistic understanding remains basic. Herein, we disclose the combined NMR spectroscopic, single-crystal X-ray crystallographic, and computational (DFT) investigation of the Au(III)-mediated alkoxycyclization of a 1,6-enyne in the presence of a bidentate pyridine-oxazoline ligand. The roles of the counterion, the solvent, and the type of Au(III) complex have been assessed. Au(III) is demonstrated to be the active catalyst in alkoxycyclization. Alkyne coordination to Au(III) involves decoordination of the pyridine nitrogen and is the rate-limiting step.

  DOI：

  10.1021/jacs.9b09108

文献信息

• On the Mechanism of Carbohydroxypalladation of Enynes. Additional Insights on the Cyclization of Enynes with Electrophilic Metal Complexes
  作者：Cristina Nevado、Lise Charruault、Véronique Michelet、Cristina Nieto-Oberhuber、M. Paz Muñoz、María Méndez、Marie-Noëlle Rager、Jean-Pierre Genêt、Antonio M. Echavarren

  DOI：10.1002/ejoc.200390110

  日期：2003.2

  Different mechanisms have been proposed for the cyclization of enynes catalyzed by electrophilic metal halides or complexes. We present evidence to indicate that the previously reported “carbohydroxypalladation” and the “hydroxycyclization catalyzed by PtII” are closely related reactions. Thus, palladium complexes formed in situ from PdCl2 and trisulfonated phosphane TPPTS or cyclic phosphite P(OCH2)3CEt

  已经提出了由亲电子金属卤化物或配合物催化的烯炔环化的不同机制。我们提供的证据表明先前报道的“碳羟基钯化”和“由 PtII 催化的羟基环化”是密切相关的反应。因此，钯配合物由作为配体的 PdCl2 和三磺化磷烷 TPPTS 或环状亚磷酸酯 P(OCH2)3CEt 原位形成，催化烯炔的甲氧基或羟基环化，其选择性类似于用 PtII 配合物观察到的选择性。氘化研究表明，PdII 对炔烃的活化促进了烯烃的反加成。
• Asymmetric Au-catalyzed domino cyclization/nucleophile addition reactions of enynes in the presence of water, methanol and electron-rich aromatic derivatives
  作者：Alexandre Pradal、Chung-Meng Chao、Maxime R. Vitale、Patrick Y. Toullec、Véronique Michelet

  DOI：10.1016/j.tet.2011.03.071

  日期：2011.6

  system is described for the asymmetric domino cyclization/functionalization reactions of functionalized 1,6-enynes in the presence of an external nucleophile. The use of (R)-4-MeO-3,5-(t-Bu)2-MeOBIHEP ligand associated with gold led to clean rearrangements implying the formal addition of an oxygen or carbon nucleophile to an alkene followed by a cyclization process. The enantiomeric excesses were highly

  描述了一种有效的Au（I）催化体系，用于在外部亲核试剂存在下官能化1,6-烯炔的不对称多米诺环化/官能化反应。与金缔合的（R）-4-MeO-3,5-（t - Bu）2 -MeOBIHEP配体的使用导致干净的重排，这意味着将氧或碳亲核体正式加成至烯烃，然后进行环化过程。对映体过量高度依赖于底物/亲核试剂的组合。在带有较大基团的基团（受阻的二酯和二砜）和受阻碳亲核试剂的情况下，可以获得很好的对映体过量，最高可达98％。
• Gold(I)-Catalyzed Cyclizations of 1,6-Enynes: Alkoxycyclizations andexo/endo Skeletal Rearrangements
  作者：Cristina Nieto-Oberhuber、M. Paz Muñoz、Salomé López、Eloísa Jiménez-Núñez、Cristina Nevado、Elena Herrero-Gómez、Mihai Raducan、Antonio M. Echavarren

  DOI：10.1002/chem.200501088

  日期：2006.2.8

  Gold(I) complexes are the most active catalysts for alkoxy- or hydroxycyclization and for skeletal rearrangement reactions of 1,6-enynes. Intramolecular alkoxycyclizations also proceed efficiently in the presence of gold(I) catalysts. The first examples of the skeletal rearrangement of enynes by the endocyclic cyclization pathway are also documented. Iron(III) is also able to catalyze exo and endo

  金（I）配合物是最有效的催化剂，用于烷氧基或羟基环化以及1,6-炔烃的骨架重排反应。在金（I）催化剂的存在下，分子内烷氧基环化也有效地进行。还记录了环内环化途径引起的炔烃骨架重排的第一个例子。铁（III）还能够催化1,6-烯炔的外切和内切骨架重排，尽管这种转化的范围更为有限。金（I）催化的环内环化反应的机理不同于在PdII，HgII或RhI催化剂存在下的机理。
• Cyclizations of Enynes Catalyzed by PtCl₂ or Other Transition Metal Chlorides:  Divergent Reaction Pathways
  作者：María Méndez、M. Paz Muñoz、Cristina Nevado、Diego J. Cárdenas、Antonio M. Echavarren

  DOI：10.1021/ja0112184

  日期：2001.10.31

  (eta2-alkyne)platinum complex. The formation of the C-C and C-O bonds takes place stereoselectively by trans addition of the electrophile derived from the alkyne and the nucleophile to the double bond of the enyne. Formation of five- or six-membered carbo- or heterocycles could be obtained from 1-en-6-ynes depending on the substituents on the alkene or at the tether. Although more limited in scope, Ru(II) and Au(III)

  1-en-6-ynes 在 PtCl2 作为催化剂存在下与醇或水反应，得到在侧链上带有烷氧基或羟基官能团的碳环。该反应通过烯烃对（η2-炔）铂络合物的抗攻击而进行。CC 和 CO 键的形成是通过将衍生自炔烃的亲电试剂和亲核试剂反式加成到烯炔的双键上而立体选择性地发生的。根据烯烃上或系链上的取代基，可以从 1-en-6-yne 形成五元或六元碳或杂环。尽管范围更有限，但 Ru(II) 和 Au(III) 氯化物也会引起烯炔的烷氧基或羟基环化。根据密度泛函理论 (DFT) 计算，发现环丙基铂卡宾配合物是该过程的关键中间体。在极性非亲核溶剂存在下，1-en-6-ynes 与 PtCl2 作为催化剂发生环异构化。DFT 计算支持铂环戊烯中间体的形成。该反应通过反式烯丙基取代基的选择性夺氢而发生。可以在 MeOH 中使用 RuCl3 或 Ru(AsPh3)4Cl2 进行含有双取代烯烃的烯炔的环异构化。
• Structure–enantioselectivity correlation in NHC–Au(I) catalysis for 1,6-enynecyclizations
  作者：Benjamin W. Gung、Michael R. Holmes、Caleb A. Jones、Ruoyu Ma、Charles L. Barnes

  DOI：10.1016/j.tetlet.2016.07.046

  日期：2016.8

  A direct correlation of the NHC ligand structure and the induced enantioselectivity has been uncovered for a series of new chiral gold(I) complexes. The Au(I)Cl complexes were identified by 1H, 13C NMR spectroscopy, and X-ray structure analysis. The corresponding activated Au(I) catalysts with a phenyl nitrile dynamic ligand are prepared and used in the catalysis of 1,6-enyne cyclization reactions

  对于一系列新的手性金（I）配合物，已经发现了NHC配体结构和诱导的对映选择性的直接相关性。通过1 H，13 C NMR光谱和X射线结构分析鉴定Au（I）Cl络合物。制备具有苯基腈动态配体的相应活化的Au（I）催化剂，并将其用于1，6-烯炔环化反应的催化中。用6％的手性NHC–Au（I）催化剂可获得高化学产率和良好的对映选择性。这些反应中的产物可达到75％ee。手性NHC配体的结构，其中邻-联苯基部分与氮原子相连，远端3,5-二烷基苯基在对映选择性中起决定性作用。