methyl 4-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl)benzoate | 1007392-17-7

• 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: methyl 4-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl)benzoate
• 英文别名: Methyl 4-[(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl]benzoate
• CAS: 1007392-17-7
• 化学式: C₁₅H₁₄O₆
• 分子量: 290.273
• InChiKey: WLVSUINXCNEVRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl)benzoate 、 丙炔 在 正丁基氯化镁 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 4-(1-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)but-2-ynyl)benzoate
  参考文献：
  名称：

  Meldrum 酸衍生受体的实用不对称共轭炔基化：获得手性 β-炔基酸

  摘要：

  炔基亲核试剂的对映选择性共轭加成一直是合成化学中长期存在的挑战。本文描述了使用辛可尼丁 (<$100/kg) 作为手性介质的 Meldrum 酸衍生受体的高度实用的不对称共轭炔基化。该过程提供了获得手性β-炔基酸的实际途径。该方法的值得注意的属性是其广泛的范围、高度的功能组兼容性和易于扩展。

  DOI：

  10.1021/ja909105s
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 、 对甲酰基苯甲酸甲酯 以 水 为溶剂， 生成 methyl 4-((2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)methyl)benzoate
  参考文献：
  名称：

  利用异丙醇作为唯一和无痕还原剂的活性烯烃的无催化剂转移加氢

  摘要：

  金属催化和有机催化转移加氢反应都广泛用于还原 C O 和 C N 键。然而，C C 键的选择性转移氢化反应仍然具有挑战性。因此，在温和条件下和在没有金属催化剂的情况下，使用容易获得且廉价的还原剂（即伯醇和仲醇）对烯烃进行化学选择性转移加氢，将标志着绿色转移加氢策略的发展取得了重大进展。本文描述的是活性烯烃的非常规无催化剂转移氢化反应，使用异丙醇作为环保还原剂和溶剂。该反应以中等至良好的收率方便地合成了多种取代的丙二酸半氧酯 （SMAHO）。机理研究指出了一种前所未有的氢键辅助转移氢化过程。

  DOI：

  10.1039/d2gc04315g

文献信息

• Synthesis and Characterization of Tricarbastannatranes and Their Reactivity in B(C₆F₅)₃-Promoted Conjugate Additions
  作者：Azadeh Kavoosi、Eric Fillion

  DOI：10.1002/anie.201500983

  日期：2015.4.27

  The synthesis and characterization of a series of tricarbastannatranes, in the solid state and in solution, are described. The structures of the complexes [N(CH2CH2CH2)3Sn](BF4), [N(CH2CH2CH2)3Sn](SbF6), [N(CH2CH2CH2)3Sn]4[(SbF6)3Cl], and [(N(CH2CH2CH2)3Sn)2OH][MeB(C6F5)3] were determined by X‐ray crystallography. Furthermore, the B(C6F5)3‐promoted conjugate addition of alkyl‐tricarbastannatranes to

  描述了一系列固态和溶液中的三碳金刚烷酯的合成和表征。配合物[N（CH 2 CH 2 CH 2）3 Sn]（BF 4），[N（CH 2 CH 2 CH 2）3 Sn]（SbF 6），[N（CH 2 CH 2 CH 2）3 Sn] 4 [（SbF 6）3 Cl]和[[N（CH 2 CH 2 CH 2）3 Sn）2 OH] [MeB（C6 F 5）3 ]通过X射线晶体学测定。此外，还研究了烷基（三氟甲氨基苯甲酸）的B（C 6 F 5）3促进的共轭加成到麦德鲁姆酸的亚苄基衍生物中，并进行了详细的机理研究。
• Enantioselective Rhodium-Catalyzed Conjugate Alkynylation of 5-Benzylidene Meldrum’s Acids with TMS-acetylene
  作者：Eric Fillion、Alexander K. Zorzitto

  DOI：10.1021/ja905336p

  日期：2009.10.21

  The enantiosetective alkynylation of benzylidene Meldrum's acids has been successfully achieved through rhodium-catalyzed addition of TMS-acetylene in the presence of bisphosphine ligand 3,5-Xylyl-MeOBIPHEP. The resulting Meldrum's acids were obtained in good yields and up to 99% enantiomeric excess. The alkynylation method is carried out under mild reactions conditions and is compatible with an array of functional groups.
• Sequential Rh(I)/Pd-Catalyzed 1,4-Addition/Intramolecular Allylation:  Stereocontrolled Construction of γ-Butyrolactones and Cyclopropanes
  作者：Eric Fillion、Sébastien Carret、Lauren G. Mercier、Vincent É. Trépanier

  DOI：10.1021/ol702613f

  日期：2008.2.1

  The rhodium-catalyzed conjugate addition of functionalized vinyltin reagents to alkylidene Meldrum's acids, followed by Pd-catalyzed intramolecular allylation, is a direct entry into vinyl-substituted gamma-lactones via O-alkylation and vinylcyclopropanes via C-alkylation.
• Chemoselective and Diastereoconvergent Cu(II)-Catalyzed Aerobic Endoperoxidation of Polycarbonyls
  作者：James Giarrusso、Dung T. Do、Jeffrey S. Johnson

  DOI：10.1021/acs.orglett.7b01225

  日期：2017.6.16

  The diastereoconvergent synthesis of spirocyclic endoperoxides using a Meldrum's acid scaffold has been accomplished by employing readily available feedstock Chemicals. Site selective C-H oxidation of the bis(beta-dicarbonyl) substrates was performed using, elemental oxygen as the stoichiometric oxidant and a commercial Cu(II) catalyst. Sequential hydrogenolysis and ionic reduction of these-endoperoxides provided fully substituted tetrahydrofurans in high-yields and diastereoselectivity.
• A joint experimental and theoretical structural study of novel substituted 2,5-dioxo-1,2,3,4,5,6,7,8-octahydroquinolines
  作者：Margarita Suárez、Estael Ochoa、Yamila Verdecia、Beatriz Pita、Lourdes Morán、Nazario Martín、Margarita Quinteiro、Carlos Seoane、JoséL Soto、Hector Novoa、Norbert Blaton、Oswald M Peters

  DOI：10.1016/s0040-4020(98)01078-3

  日期：1999.1

  A series of substituted 2,5-dioxo-1,2,3,4,5,5,7,8-octahydroquinolines have been synthesised from Meldrum's acid and dimedone in the presence of different aldehydes by following an approach similar to the one developed by Hantzch. The structure of these compounds has been thoroughly studied by X-ray crystallographic analysis and semiempirical (AM1) and ab initio (HF/3-21G) methods, and two favoured conformations are possible. A good agreement is found between the theoretical and experimental values. The most stable conformation (A) in the solid state is also that favoured in solution, according to the proton coupling constant determined from Karplus' and Altona's equations and H-1 NMR spectroscopic experiments. (C) 1998 Elsevier Science Ltd. All rights reserved.