dimethyl (S)-[(E)-1,3-diphenylprop-2-en-1-yl](methyl)malonate | 96482-63-2

• 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: dimethyl (S)-[(E)-1,3-diphenylprop-2-en-1-yl](methyl)malonate
• 英文别名: (E)-dimethyl 2-(1’,3’-diphenylallyl)-2-methylmalonate；dimethyl 2-((E)-(S)-1,3-diphenyl-allyl)-α-methylmalonate；(S,E)-methyl 2-carbomethoxy-2-methyl-3,5-diphenylpent-4-enoate；methyl (E)-2-carbomethoxy-2-methyl-3,5-diphenylpent-4-enoate；methyl (S)-2-carbomethoxy-2-methyl-3,5-diphenylpent-4-enoate；(S)-dimethyl (1,3-diphenylprop-2-en-1-yl)methylmalonate；dimethyl 2-[(E,1S)-1,3-diphenylprop-2-enyl]-2-methylpropanedioate
• CAS: 96482-63-2；136892-39-2；96482-66-5
• 化学式: C₂₁H₂₂O₄
• 分子量: 338.403
• InChiKey: OBBIUYHSXNRJGV-JJJPLKNQSA-N

物化性质

• 沸点：
  439.7±45.0 °C(Predicted)
• 密度：
  1.135±0.06 g/cm3(Predicted)

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 dimethyl (S)-[(E)-1,3-diphenylprop-2-en-1-yl](methyl)malonate
  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

• A <scp>d</scp> -Camphor-Based Schiff Base as a Highly Efficient N,P Ligand for Enantioselective Palladium-Catalyzed Allylic Substitutions
  作者：Qiao-Ling Liu、Weifeng Chen、Qun-Ying Jiang、Xing-Feng Bai、Zhifang Li、Zheng Xu、Li-Wen Xu

  DOI：10.1002/cctc.201600084

  日期：2016.4.20

  New Schiff bases derived from chiral d‐camphor were determined to be effective phosphine ligands for the asymmetric palladium‐catalyzed allylic alkylation of activated methylene compounds, the allylic etherification of alcohols, and the allylic amination of primary amines or secondary amines, in which the corresponding products with various functional groups were achieved in good yields with excellent

  从手性衍生的新的席夫碱d -樟脑被确定为用于活化的亚甲基化合物的不对称钯催化的烯丙基烷基化，醇的烯丙基醚化，和伯胺或仲胺的烯丙基胺化，其中，对应的有效的膦配体具有良好收率和优异的对映选择性（高达> 99％ee），可以得到具有各种官能团的产物 。值得注意的是，衍生自席夫碱L2的钯催化剂提供了迄今为止报道的最高水平的对映选择性，可用于烯丙基取代反应，包括烯丙基醚化和烯丙基胺化反应，从而揭示了d的特殊作用。钯催化的烯丙基取代反应中源自樟脑的席夫碱。
• 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％  。
• Imidate-Phosphanes as Highly Versatile N,P Ligands and Their Application in Palladium-Catalyzed Asymmetric Allylic Alkylation Reactions
  作者：Timothy Noël、Katrien Bert、Erik Van der Eycken、Johan Van der Eycken

  DOI：10.1002/ejoc.201000238

  日期：2010.7

  Chiral imidate-phosphanes were developed as a new type of N,P ligands. These ligands are easily accessible through a one-step procedure starting from a commercially available chiral aminophosphane and an imidate precursor. Excellent performance of the catalyst system was observed with various carbon nucleophiles in the Pd(0)-catalyzed asymmetric allylic alkylation (up to 99% yield and >99 % ee). Moreover

  手性亚胺酯膦作为一种新型的 N,P 配体被开发出来。这些配体可通过从市售手性氨基膦和亚胺酸酯前体开始的一步程序轻松获得。在 Pd(0) 催化的不对称烯丙基烷基化反应中，使用各种碳亲核试剂观察到催化剂体系的优异性能（产率高达 99% 和 >99% ee）。此外，在更困难的线性无阻碍底物和环状底物的烯丙基烷基化中也可以获得良好到优异的对映选择性，表明这种新的催化剂体系具有广泛的底物范围。