dimethyl (S)-2-(1-(4-(trifluoromethyl)phenyl)allyl)malonate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: dimethyl (S)-2-(1-(4-(trifluoromethyl)phenyl)allyl)malonate
• 英文别名: dimethyl 2-[(1S)-1-[4-(trifluoromethyl)phenyl]prop-2-enyl]propanedioate
• 化学式: C₁₅H₁₅F₃O₄
• 分子量: 316.277
• InChiKey: LBZFWDSDFOAYKZ-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  丙二酸二甲酯 、 1-(4-(trifluoromethyl)phenyl)allyl acetate 在 (2,2,6,6-tetramethyl-3,5-heptanedionate)Rh(ethylene)2 (S,R)-axial-phox 、 caesium carbonate 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以97%的产率得到dimethyl (S)-2-(1-(4-(trifluoromethyl)phenyl)allyl)malonate
  参考文献：
  名称：

  High Enantioselectivity in Rhodium-Catalyzed Allylic Alkylation of 1-Substituted 2-Propenyl Acetates

  摘要：

  [GRAPHICS]Rhodium-catalyzed asymmetric allylic alkylation of 1-substituted 2-propenyl acetates with dimethyl malonate proceeded with high enantioselectivity in the presence of cesium carbonate as a base and a rhodium catalyst generated from Rh(dpm)(C2H4)(2) (dpm = dipivaloylmethanato) and a chiral phosphino-oxazoline whose basic skeleton is axially chiral binaphthyl to give branch alkylation products in greater than 90% ee.

  DOI：

  10.1021/ol0343562

文献信息

• Phosphoramidite Ligands in Iridium-Catalyzed Allylic Substitution
  作者：Damien Polet、Alexandre Alexakis、Karine Tissot-Croset、Clémence Corminboeuf、Klaus Ditrich

  DOI：10.1002/chem.200501180

  日期：2006.4.24

  A new phosphoramidite ligand was used in the iridium-catalyzed allylic substitution reaction. This permitted high regio- and enantioselectivities on a wide variety of substrates and nucleophiles. Because of the stereospecificity of the reaction obtained by using branched substrates, a kinetic resolution reaction was attempted. The origin of the impressive efficiency of this ligand in terms of kinetics

  在铱催化的烯丙基取代反应中使用了新的亚磷酰胺配体。这允许在多种底物和亲核试剂上具有很高的区域和对映选择性。由于通过使用支链底物获得的反应的立体特异性，尝试进行动力学拆分反应。详细研究了该配体在动力学方面令人印象深刻的效率的起因，以及取代基在胺部分邻位中的作用。
• Very Efficient Phosphoramidite Ligand for Asymmetric Iridium-Catalyzed Allylic Alkylation
  作者：Alexandre Alexakis、Damien Polet

  DOI：10.1021/ol048607y

  日期：2004.9.1

  [reaction: see text] Linear or branched allylic carbonates or acetates undergo enantioselective iridium-catalyzed allylic substitution with sodium malonate. The reaction is wide in scope and affords the branched product in high yield and with high regio- (up to >99:1) and enantioselectivity (up to 98%). Ten aromatic or aliphatic substrates were successfully tested.

  [反应：见正文]线性或支链的烯丙基碳酸酯或乙酸酯经过丙二酸钠对映选择性铱催化的烯丙基取代。该反应范围广，并以高收率和高区域选择性（最高> 99：1）和对映选择性（最高98％）提供了支链产物。成功测试了十种芳族或脂族底物。
• Iridium/<i>N</i>-Heterocyclic Carbene Complex-Catalyzed Intermolecular Allylic Alkylation Reaction
  作者：Can-Can Bao、Dong-Song Zheng、Xiao Zhang、Shu-Li You

  DOI：10.1021/acs.organomet.8b00762

  日期：2018.12.24

  N-Heterocyclic carbenes (NHCs) were found to be suitable ligands in Ir-catalyzed intermolecular allylic alkylation reaction. In the presence of a catalyst derived from [Ir(dncot)Cl]2 (dncot = dinaphthocyclooctatetraene) and triazolium salt L7, the alkylation products from the reaction of aryl allyl carbonates with sodium dialkyl malonates could be obtained in 85–99% yields favoring the formation of

  发现N-杂环卡宾（NHC）是Ir催化的分子间烯丙基烷基化反应中的合适配体。在[Ir（dncot）Cl] 2（dncot =二萘环辛酸酯四烯）和三唑鎓盐L7衍生的催化剂存在下，芳基烯丙基碳酸酯与二烷基丙二酸钠的反应可得到烷基化产物，收率高达85-99％，形成支链产物（90/10→> 99/1 b / l）。此外，手性二氢异喹啉型NHC（DHIQ-NHC）（L8）已成功应用于Ir催化的不对称烯丙基烷基化反应中。对于广泛的底物，获得了优异的对映选择性和中等的区域选择性。
• An Improved Class of Phosphite-Oxazoline Ligands for Pd-Catalyzed Allylic Substitution Reactions
  作者：Maria Biosca、Joan Saltó、Marc Magre、Per-Ola Norrby、Oscar Pàmies、Montserrat Diéguez

  DOI：10.1021/acscatal.9b01166

  日期：2019.7.5

  for generation of Pd/phosphite-oxazoline catalysts containing an alkyl backbone chain has been successfully applied to Pd-catalyzed allylic substitution reactions. By carefully selecting the substituents at both the alkyl backbone chain and the oxazoline of the ligand, as well as the configuration of the biaryl phosphite group, high activities (TOF > 8000 mol substrate × (mol Pd × h)−1) and excellent

  包含烷基主链的Pd /亚磷酸酯-恶唑啉催化剂的制备方法已成功地应用于Pd催化的烯丙基取代反应。通过仔细选择配体的烷基主链和恶唑啉上的取代基以及亚磷酸亚芳基酯的构型，可获得高活性（TOF> 8000 mol底物×（mol Pd×h）-1）和具有多种C-，O-和N-亲核试剂（总共73个取代产物）的许多受阻和不受阻底物均实现了出色的对映选择性（ee高达99％）。此外，对关键的Pd-烯丙基配合物的DFT和NMR研究使我们能够更好地了解实验观察到的优异对映选择性的起源。Pd /亚磷酸酯-恶唑啉催化剂的有用应用已通过许多具有手性立体中心的手性碳环的合成，通过涉及Pd-烯丙基取代和1,6-烯炔环化或Pauson-Khand烯炔环化的简单顺序反应得到了证明。
• Enantioselective Ir-Catalyzed Allylic Alkylation of Racemic Allylic Alcohols with Malonates
  作者：Chun-Yan Meng、Xiao Liang、Kun Wei、Yu-Rong Yang

  DOI：10.1021/acs.orglett.8b04143

  日期：2019.2.1

  Ir-catalyzed enantioselective allylic alkylation of branched racemic allylic alcohols with malonates is described. Enabled by Carreira’s chiral Ir/(P, olefin) complex, the method described allows allylic substitution with various aromatic alcohols and malonates with excellent enantioselectivity. The malonates could be used directly as efficient nucleophiles without the need of preactivation.

  描述了用丙二酸酯对支链外消旋烯丙基醇进行Ir催化的对映选择性烯丙基烷基化。通过Carreira的手性Ir /（P，烯烃）配合物，所描述的方法可以用各种芳族醇和丙二酸酯进行烯丙基取代，并具有出色的对映选择性。丙二酸酯可直接用作有效的亲核试剂，而无需预活化。