dimethyl-4-(4-methoxyphenyl)-4-methyl-3,4-dihydronaphthalene-2,2-(1H)-dicarboxylate | 1402050-89-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dimethyl-4-(4-methoxyphenyl)-4-methyl-3,4-dihydronaphthalene-2,2-(1H)-dicarboxylate
• 英文别名: Dimethyl 4-(4-methoxyphenyl)-4-methyl-1,3-dihydronaphthalene-2,2-dicarboxylate
• CAS: 1402050-89-8
• 化学式: C₂₂H₂₄O₅
• 分子量: 368.43
• InChiKey: KYFZNIJBYMYYEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 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 2-benzyl-2-(prop-2-yn-1-yl)malonate 、 苯甲醚 在 [Ga(I)(PhF)2]⁺[Al(OR^F)4]^- 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以81%的产率得到dimethyl-4-(4-methoxyphenyl)-4-methyl-3,4-dihydronaphthalene-2,2-(1H)-dicarboxylate
  参考文献：
  名称：

  低价阳离子镓（I）配合物作为π酸的催化用途

  摘要：

  首次使用低价Ga（I）物种进行了与π-路易斯酸催化有关的烯烃和炔烃底物的转化。[Ga（I）（PhF）2 ] + [Al（OR F）4 ] -和二氯化镓（即[Ga（I）] + [GaCl 4 ] -）被证明是有效的环异构化催化剂，Friedel-Crafts反应，转移氢化和还原性氢芳基化。将它们的活性与更常见的Ga（III）配合物进行比较。这项研究表明，即使容易获得但仍被忽视的二氯化镓盐也可能比三氯化镓或其他Ga（III）物种具有更高的活性π-路易斯酸催化剂。

  DOI：

  10.1002/adsc.201701081

文献信息

• Non-Innocent Behavior of Substrate Backbone Esters in Metal-Catalyzed Carbocyclizations and Friedel–Crafts Reactions of Enynes and Arenynes
  作者：Bastien Michelet、Guillaume Thiery、Christophe Bour、Vincent Gandon

  DOI：10.1021/acs.joc.5b02052

  日期：2015.11.6

  of metal-catalyzed carbocyclization reactions. The non-innocent role of the ester functionality in lowering the activation barrier of the key step of the gallium- and indium-catalyzed cycloisomerization of 1,6-enynes is revealed. In the case of the gallium-catalyzed hydroarylation of arenynes, the esters in the tether can deprotonate the Wheland intermediate, thus avoiding more energetically demanding

  根据DFT计算和实验结果，我们表明有机基团主链中酯基的存在会影响金属催化的碳环化反应的机理。揭示了酯官能团在降低镓和铟催化的1，6-烯炔的环异构化关键步骤的活化势垒方面的非清白作用。在芳烃的镓催化加氢芳基化的情况下，系链中的酯可以使Wheland中间体去质子化，从而避免了更强烈地要求[1,3]-或[1,2] / [1,2] -H的转变。作为镓催化的Friedel-Crafts烷基化，不同寻常的协调一致的小号Ë已经计算出涉及酯的Ar机理。最后，计算证据表明丙酸甲酯的酯基能够在铂催化的分子内氢芳基化反应中形成发散机理。
• Dibromoindium(<scp>iii</scp>) cations as a π-Lewis acid: characterization of [IPr·InBr₂][SbF₆] and its catalytic activity towards alkynes and alkenes
  作者：Bastien Michelet、Jean-Rémy Colard-Itté、Guillaume Thiery、Régis Guillot、Christophe Bour、Vincent Gandon

  DOI：10.1039/c5cc00740b

  日期：——

  [IPr[middle dot]InBr2][SbF6] (2) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) has been synthesized, characterized in the solid state, and used as catalyst.

  合成了[IPr [Inb 2 InBr 2 ] [SbF 6 ]（2）（IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基），以固态表征，并用作催化剂。
• Cationic Gallium(III) Halide Complexes: A New Generation of π-Lewis Acids
  作者：Shun Tang、Julien Monot、Ahmad El-Hellani、Bastien Michelet、Régis Guillot、Christophe Bour、Vincent Gandon

  DOI：10.1002/chem.201201202

  日期：2012.8.13

  Ga‐neration X: Well‐defined neutral and cationic gallium(III) halide complexes have been synthesized and evaluated in catalysis. Both the (NHC)GaX3/AgSbF6 catalytic mixture and isolated (NHC)GaX2+ species function as exquisite π‐Lewis acids in typical GaX3‐catalyzed reactions (see scheme). The cationic complexes are more active than GaX3 and yet more resistant to hydrolysis, which allows lower catalytic

  生成X：合成明确的中性和阳离子卤化镓（III）配合物并在催化中进行了评估。在典型的GaX 3催化反应中，（NHC）GaX 3 / AgSbF 6催化混合物和分离出的（NHC）GaX 2 +物质均充当精致的π-路易斯酸（参见方案）。阳离子络合物比GaX 3更具活性，但对水解的抵抗力更高，从而可降低催化负载量并加快反应速度。
• Structure, Stability, and Catalytic Activity of Fluorine-Bridged Complexes IPr·GaCl₂(μ-F)EF_<i>n</i>–1 (EF_<i>n</i>^– = SbF₆^–, PF₆^–, or BF₄^–)
  作者：Christophe Bour、Julien Monot、Shun Tang、Régis Guillot、Jonathan Farjon、Vincent Gandon

  DOI：10.1021/om4012054

  日期：2014.1.27

  Fluorine-bridged NHC-gallium(III) complexes of the type IPr center dot GaCl2(mu-F)EFn-1 [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, and EFn = SbF6 or BF4] have been synthesized and characterized in solution and in the solid state. The [BF4](-) adduct readily decomposes into gallium fluorides of the type [IPr center dot GaClmF3-m] (m = 0, 1, or 2) with release of gaseous BF3. These results corroborate the trend observed in IPr center dot GaCl3/AgEFn-catalyzed reactions in which a strong anion effect exists.
• Relationship between Gallium Pyramidalization in L·GaCl₃ Complexes and the Electronic Ligand Properties
  作者：Ahmad El-Hellani、Julien Monot、Shun Tang、Régis Guillot、Christophe Bour、Vincent Gandon

  DOI：10.1021/ic401817g

  日期：2013.10.7

  Six new molecular GaCl3 adducts of electron rich compounds of the carbone (carbodiphosphorane, tetraaminoallene) and cyclic alkyl amino carbene (CAAC) families have been synthesized and characterized by X-ray crystallography. The sum of their Cl-Ga-Cl angles has been compared to those of 20 other complexes exhibiting various oxygen-, nitrogen-, phosphorus-, and carbon-donor ligands for which good quality X-ray analyses have been reported. The pyramidalization of the GaCl3 moiety in L center dot GaCl3 complexes has been checked against the computed antisymmetric stretching of the Ga-Cl bonds. It has also been compared to the symmetric stretching of the C-O bonds of the corresponding L center dot Ni(CO)(3) complexes (Tolman Electronic Parameter). On this basis, a relationship between the pyramidalization observed in the gallium complexes and the electronic ligand properties has been established.