(R,E)-dimethyl 2-(1,3-diphenylallyl)-2-methylmalonate

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (R,E)-dimethyl 2-(1,3-diphenylallyl)-2-methylmalonate
• 英文别名: dimethyl (R,E)-2-(1,3-diphenylallyl)-2-methylmalonate；dimethyl 2-[(E,1R)-1,3-diphenylprop-2-enyl]-2-methylpropanedioate
• 化学式: C₂₁H₂₂O₄
• 分子量: 338.403
• InChiKey: OBBIUYHSXNRJGV-LGHUBQEGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  反-1,3-二苯基-2-丙稀-1-醇 在 bis(η3-allyl-μ-chloropalladium(II)) (R)-4,4'-bis(trimethylsilyl)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 (R,E)-dimethyl 2-(1,3-diphenylallyl)-2-methylmalonate
  参考文献：
  名称：

  Applications of 4,4‘-(Me₃Si)₂-BINAP in Transition-Metal-Catalyzed Asymmetric Carbon−Carbon Bond-Forming Reactions

  摘要：

  A recently developed BINAP derivative with trimethylsilyl substituents on the 4- and 4 '-positions of the binaphthyl skeleton, 2,2 '-bis-(diphenylphosphino)-4,4 '-bis(trimethylsilyl)-1,1 '-binaphthyl (tms-BINAP), was used in a variety of transition-metal-catalyzed asymmetric carbon-carbon bond-forming reactions. In pi-allylpalladium-mediated reactions, tms-BINAP gave better enantioselectivity than the unsubstituted BINAP, and the origin of the improved enantioselectivity was gained from an X-ray structural study of [Pd(eta(3)-C3H5)((R)-tms-BINAP)]CIO4.

  DOI：

  10.1021/ol050834s

文献信息

• Conformational Preferences of a Tropos Biphenyl Phosphinooxazoline–a Ligand with Wide Substrate Scope
  作者：Rosalba Bellini、Marc Magre、Maria Biosca、Per-Ola Norrby、Oscar Pàmies、Montserrat Diéguez、Christina Moberg

  DOI：10.1021/acscatal.5b02766

  日期：2016.3.4

  palladium-catalyzed allylic substitutions of a wide range of substrate types and nucleophiles using a bidentate ligand composed of oxazoline and chirally flexible biaryl phosphite elements. This unusually wide substrate scope is shown by experimental and theoretical studies of its η3-allyl and η2-olefin complexes not to be a result of configurational interconversion of the biaryl unit, since the ligand

  使用由恶唑啉和手性柔性亚芳基亚磷酸酯元素组成的双齿配体，在钯催化的多种底物类型和亲核试剂的烯丙基取代中观察到极好的对映选择性。这种不寻常的广泛的底物范围通过的实验和理论研究显示出其η 3 -烯丙基，η 2烯烃络合物不被二芳基单元的构型相互转换的结果，由于在所有反应中配位体采用一个š一个，小号与钯配位的构型，而是配体使底物结合口袋适应反应底物大小的能力。该能力还可以解释其在其他类型的催化过程中的优异性能。
• Novel Chiral Diamino-Oligothiophenes as Valuable Ligands in Pd-Catalyzed Allylic Alkylations. On the “Primary” Role of “Secondary” Interactions in Asymmetric Catalysis
  作者：Vincenzo Giulio Albano、Marco Bandini、Manuela Melucci、Magda Monari、Fabio Piccinelli、Simona Tommasi、Achille Umani-Ronchi

  DOI：10.1002/adsc.200505109

  日期：2005.10

  A new class of chiral C2-symmetrical diamino-oligothiophenes is described to be effective in catalyzing Pd-mediated asymmetric allylic alkylations in a highly enantioselective manner. The combination of experimental as well as crystallographic evidence revealed the key role played by sulfur-based heteroaromatic rings in the stereodiscriminating step of the procedure. In particular, unprecedented non-covalent

  一种新型的手性C 2对称的二氨基-低聚噻吩被描述为以高对映选择性的方式有效催化Pd介导的不对称烯丙基烷基化反应。实验和晶体学证据的结合揭示了基于硫的杂芳族环在该方法的立体鉴别步骤中所起的关键作用。特别是，内部噻吩与金属中心之间空前的非共价二次相互作用被证明对于创造必要的立体化学环境至关重要，以确保出色的化学和光学收率。
• New chiral diamino-bis(tert-thiophene): an effective ligand for Pd- and Zn-catalyzed asymmetric transformations
  作者：Marco Bandini、Manuela Melucci、Fabio Piccinelli、Riccardo Sinisi、Simona Tommasi、Achille Umani-Ronchi

  DOI：10.1039/b711666g

  日期：——

  Enantiomerically pure diamino-bis(tert-thiophene) 1b proved to be a valuable and flexible chiral ligand for Pd- and Zn-catalyzed transformations, allowing for high levels of stereocontrol in asymmetric allylic alkylation (ee up to 99%) and hydrosilylations of prochiral carbonyls (ee up to 97%).

  对映体纯的二氨基双(叔噻吩) 1b被证明是一种有价值的、灵活的手性配体，适用于Pd催化和Zn催化的反应，能够在不对称烯丙基烷化（ee值高达99%）和前手性羰基的氢硅化反应（ee值高达97%）中实现高水平的立体控制。
• Synthetic and mechanistic studies in enantioselective allylic substitutions catalysed by palladium complexes of a modular class of axially chiral quinazoline-containing ligands
  作者：Anne-Marie Carroll、Mary McCarthy、Patrick M. Lacey、Cormac P. Saunders、David J. Connolly、Annette Farrell、Balaji V. Rokade、Richard Goddard、Peter Fristrup、Per-Ola Norrby、Patrick J. Guiry

  DOI：10.1016/j.tet.2019.130780

  日期：2020.1

  The application of palladium complexes of a modular series of axially chiral phosphinamine ligands, the Quinazolinaps, to the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and methyl dimethyl malonate is described. Complete conversions and enantiomeric excesses of up to 91% were obtained. To elucidate the solution structure of these complexes and their dynamic

  描述了模块化系列的轴向手性次膦胺配体喹唑啉类的钯配合物在1，3-二苯基-2-丙烯基乙酸乙酸酯与丙二酸二甲酯和丙二酸二甲酯的对映选择性烷基化中的应用。获得完全转化和对映体过量至多91％。为了阐明这些络合物的溶液结构及其动态行为，进行了2D COZY和NOESY NMR实验。衍生自具有两个Pd 3 Cl 5的2-苯基喹唑啉酮的Palladacycle的X射线晶体结构显示了单位。还进行了计算研究以对非对映异构体比率进行定性预测。然后根据光谱数据和理论数据对观察到的对映选择性进行合理化处理。通过对烯丙基反式转化为主要非对映异构中间体的磷供体原子进行亲核攻击，可以最好地解释所获得的催化结果。
• Turning the Nitrogen Atoms of an Ar₂ P−CH₂ −N−N−CH₂ −PAr₂ Motif into Uniquely Configured Stereocenters: A Novel Diphosphane Design for Asymmetric Catalysis
  作者：Eva Diehl née Knobloch、Reinhard Brückner

  DOI：10.1002/chem.201706160

  日期：2018.3.7

  Hexahydropyridazines with CH2PAr2 groups at both N atoms are newly designed 1,4‐diphosphanes and were synthesized for the first time. Their N atoms assume a single configuration under the influence of stereocenters at C‐5 and C‐6. In the solid state, these N‐atoms bind the CH2PAr2 substituents axially. Combined with Pd0, N,N′‐chiral diphosphanes of this kind catalyzed Tsuji–Trost type allylations of dialkyl malonates

  在两个N原子上均具有CH 2 PAr 2基团的六氢哒嗪是新设计的1,4-二膦烷，是首次合成。它们的N原子在C-5和C-6的立体中心的影响下呈单一构型。在固态下，这些N原子轴向结合CH 2 PAr 2取代基。与此类的Pd 0，N，N'-手性二膦烷结合，可有效地与乙酸外消旋1,3-二苯基烯丙基乙酸酯催化二甲基丙二酸酯的Tsuji-Trost型烯丙基化，且ee高达91％  。