[PdCl(3,4-dimethyl-1-phenylarsole)((S)-[1-(dimethylamino)ethyl]naphthalene)]

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: [PdCl(3,4-dimethyl-1-phenylarsole)((S)-[1-(dimethylamino)ethyl]naphthalene)]
• 英文别名: chloropalladium(1+);(1S)-N,N-dimethyl-1-(2H-naphthalen-2-id-1-yl)ethanamine;3,4-dimethyl-1-phenylarsole
• 化学式: C₂₆H₂₉AsClNPd
• 分子量: 572.318
• InChiKey: VRPLMZOARYBALU-XVSRHIFFSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.32
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  silver perchlorate 、 [PdCl(3,4-dimethyl-1-phenylarsole)((S)-[1-(dimethylamino)ethyl]naphthalene)] 以 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Palladium-promoted asymmetric cycloaddition reaction of arsole via an unusual exo–endo stereochemically controlled method

  摘要：

  Asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and ethyl vinyl ketone was promoted by the palladium complex containing ortho-metalated (S)-[1-(dimethylamino) ethyl] naphthalene as the chiral auxiliary. The keto group in the resulting arsanorbornene cycloadducts could be located stereospecifically in the endo or exo position by controlling the electronic properties of the organopalladium promoter. In the intermolecular cycloaddition reaction, a pair of separable diastereomeric palladium complexes was obtained in the ratio of 2:1. In the intramolecular process, however, only one As-O bidentate arsanorbornene palladium complex was produced stereoselectively. The arsenic-elimination reaction was readily observed on the corresponding endo- and exo-ketoarsine ligands. The absolute configuration and the coordination property of the enantiomerically pure endo-cycloadduct had been established by single-crystal X-ray analysis. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2014.01.019

文献信息

• Steric effects on the control of endo/exo-selectivity in the asymmetric cycloaddition reaction of 3,4-dimethyl-1-phenylarsole
  作者：Mengtao Ma、Ruifeng Lu、Sumod A. Pullarkat、Weiqiao Deng、Pak-Hing Leung

  DOI：10.1039/b924613d

  日期：——

  The asymmetric cycloaddition reactions of 3,4-dimethyl-1-phenylarsole and (Z/E)-diphenyl-1-propenylphosphine/diphenyl-1-styrylphosphine promoted by a chiral organopalladium(II) complex derived from (S)-[1-(dimethylamino)ethyl]naphthalene proceeded stereoselectively to generate different exo/endo-products. The reactions involving the (Z/E)-methyl substituted phosphines gave the individual optically

  芳烃的不对称环加成反应 3,4-二甲基-1-苯基芳醚和（Z /E）-二苯基-1-丙烯基膦/二苯基-1-苯乙烯基膦 由手性促进 有机钯（II） 复杂源于 （S）-[1-（二甲基氨基）乙基]萘进行立体选择性生成不同的exo /内产物。涉及（Z /E）-甲基取代的膦以非常高的立体选择性（33：1）给出了单独的光学纯的外-和内-环加合物。然而，当甲基代替通过pH部分两者（ž /E）-苯基取代的膦产生的相同内切在单一步骤1.每个反应中产生五个新的手性中心（其中四个是空间独立的）和以高收率获得所有三个光学纯作为-P配体heterobidentate：在15一个立体选择性-cycloadduct 。涉及的转化机制外切-到远藤-product进行了研究通过密度泛函理论计算。计算结果与实验观察到的内/外选择性一致。
• Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S Ligand
  作者：Mengtao Ma、Sumod A. Pullarkat、Yongxin Li、Pak‐Hing Leung

  DOI：10.1002/ejic.200901203

  日期：2010.4

  The cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphane sulfide was promoted by chiral palladium and platinum complexes containing ortho-metalated (S)-[1-(dimethylamino)ethyl]naphthalene. They exhibited similar stereoselectivity; the palladium cycloadducts could not be separated via column chromatography and fractional crystallization, however, the corresponding platinum

  含有邻位金属化 (S)-[1-(二甲氨基)乙基]萘的手性钯和铂配合物促进了 3,4-二甲基-1-苯基亚甲醚和二苯基乙烯基膦硫化物之间的环加成反应。它们表现出相似的立体选择性；钯环加合物无法通过柱色谱和分步结晶进行分离，但是，相应的铂配合物可以成功转化为对映体纯的对应物。在释放的游离 As/P=S 二齿配体上观察到正式的亚芳基消除反应。
• Metal Effects on the Asymmetric Cycloaddition Reaction between 3,4-Dimethyl-1-phenylarsole and Diphenylvinylphosphine Oxide
  作者：Mengtao Ma、Sumod A. Pullarkat、Mingjun Yuan、Na Zhang、Yongxin Li、Pak-Hing Leung

  DOI：10.1021/om900530q

  日期：2009.8.24

  reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine oxide in high stereoselectivity (only one isomer). However, the neutral dichloro palladium complex obtained upon removal of the auxiliary is very unstable and instantly decomposed to produce the arsenic elimination reaction product (3,4-dimethyl-2,4-cyclohexadienyl)diphenylphosphine oxide. However when the same reaction was promoted

  含原金属的有机钯配合物（S）-[1-（二甲基氨基）乙基]萘作为手性助剂已成功地用于促进3,4-二甲基-1-苯基芳醚与二苯基乙烯基氧化膦之间的不对称环加成反应（仅一种异构体）。但是，除去辅助剂后得到的中性二氯钯络合物非常不稳定，并立即分解产生砷消除反应产物（3，4-二甲基-2，4-环己二烯基）二苯基氧化膦。然而，当类似的铂络合物促进相同的反应时，仅再次获得一种立体异构体，但所得的二氯铂络合物在固态和溶液中均非常稳定，并以As-O二齿的形式配位至铂中心配体，由1确认1 H NMR和单晶X射线分析。通过用氰化钾水溶液处理配合物，可以很容易地从二氯铂配合物中释放出对映体纯的As͡P═O异双齿配体。
• Template effects on the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine and their arsenic elimination reaction
  作者：Mengtao Ma、Sumod A. Pullarkat、Ke Chen、Yongxin Li、Pak-Hing Leung

  DOI：10.1016/j.jorganchem.2009.01.044

  日期：2009.5

  interesting selective cleavage of one As–C bond in the norbornene skeleton and subsequent rearrangements within the skeletal framework. The molecular structure of the diiodo product has been confirmed by X-ray crystallography. Structural analysis showed that in addition to the normal As–P five-membered ring, there is one new five-membered ring containing As–O bond being formed during the course of the reaction

  含有邻金属化的（S）-[1-（二甲基氨基）乙基]萘作为手性模板的有机钯配合物被用于促进3，4-二甲基-1-苯基芳基与二苯基乙烯基膦之间的不对称环加成反应。已经证明，结合萘胺的手性模板比基于苄胺的类似物更有效，如立体选择性和反应速率的显着改善所证明的。然而，当不使用手性模板时，反式-[PdI 2（3,4-二甲基-1-苯基芳基）2 ]与反式-[PdI 2（二苯基乙烯基膦）2由于降冰片烯骨架中一个As–C键的选择性裂解以及随后在骨架骨架中的重排而产生了一种结构新颖的二碘配合物。二碘代产物的分子结构已经通过X射线晶体学证实。结构分析表明，除了正常的As-P五元环外，在反应过程中还形成了一个新的含As-O键的五元环，以及另一个带有羟基的七元环。
• Palladium-promoted asymmetric cycloaddition reaction of arsole via an unusual exo–endo stereochemically controlled method
  作者：Mengtao Ma、Zhijuan Yu、Lijun Zhu、Sumod A. Pullarkat、Pak-Hing Leung

  DOI：10.1016/j.jorganchem.2014.01.019

  日期：2014.4

  Asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and ethyl vinyl ketone was promoted by the palladium complex containing ortho-metalated (S)-[1-(dimethylamino) ethyl] naphthalene as the chiral auxiliary. The keto group in the resulting arsanorbornene cycloadducts could be located stereospecifically in the endo or exo position by controlling the electronic properties of the organopalladium promoter. In the intermolecular cycloaddition reaction, a pair of separable diastereomeric palladium complexes was obtained in the ratio of 2:1. In the intramolecular process, however, only one As-O bidentate arsanorbornene palladium complex was produced stereoselectively. The arsenic-elimination reaction was readily observed on the corresponding endo- and exo-ketoarsine ligands. The absolute configuration and the coordination property of the enantiomerically pure endo-cycloadduct had been established by single-crystal X-ray analysis. (C) 2014 Elsevier B.V. All rights reserved.