3,4-dimethyl-1-phenylarsole | 165612-45-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4-dimethyl-1-phenylarsole
• CAS: 165612-45-3
• 化学式: C₁₂H₁₃As
• 分子量: 232.157
• InChiKey: QVORYJYPVKEXBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.37
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,4-dimethyl-1-phenylarsole 以 二氯甲烷 、 丙酮 为溶剂， 生成 trans-[PdI2(3,4-dimethyl-1-phenylarsole)2]
  参考文献：
  名称：

  模板对3,4-二甲基-1-苯基arsole与二苯基乙烯基膦之间不对称环加成反应及其除砷反应的影响

  摘要：

  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。

  DOI：

  10.1016/j.jorganchem.2009.01.044

文献信息

• 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。
• Novel Stereochemistry, Reactivity, and Stability of an Arsenic Heterocycle in a Metal-Promoted Asymmetric Cycloaddition Reaction
  作者：Mengtao Ma、Sumod A. Pullarkat、Yongxin Li、Pak-Hing Leung

  DOI：10.1021/ic701419j

  日期：2007.10.1

  The organopalladium complex containing ortho-metalated (S)-[1-(dimethylamino)ethyl]phenylene as the chiral auxiliary has been used as the chiral template to promote the asymmetric cycloaddition reaction between diphenylvinylphosphine and 3,4-dimethyl-1-phenylarsole. A diphenylphosphino-substituted asymmetrical heterobidentate arsanorbomene (As-P) ligand was obtained stereoselectively on the chiral palladium template in moderate yield. The chiral benzylamine auxiliary could be removed chemoselectively from the template by treatment with HCI to produce the neutral complex [(As-P)PdCl2]- In contrast to their reported P-P analogue, the arsenic donor in the dichloro complex could be eliminated stereospecifically under mild reaction conditions to generate the corresponding 1-(diphenylphosphino)-3,4-dimethyl-2,4-cyclohexadiene, which remained as a bidentate ligand at the PdCl2 unit via phosphorus and the n(2)-C-4-C-5 double bond. The arsenic-elimination process was found to be influenced by the halo ligand in [(As-P)PdX2]. A similar process was observed with the analogous dibromo complex, but the corresponding diiodo species did not show similar reactivity. All of the novel As-Pd complexes have been characterized by X-ray crystallography.
• Ashe III, Arthur J.; Al-Ahmad, Saleem; Pilotek, Steffen, Organometallics, 1995, vol. 14, # 6, p. 2689 - 2698
  作者：Ashe III, Arthur J.、Al-Ahmad, Saleem、Pilotek, Steffen、Puranik, Dhananjay B.、Elschenbroich, Christoph、Behrendt, Andreas

  DOI：——

  日期：——
• 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。