(1Z)-1,2-bis(butylsulfanyl)-1-hexene | 1032738-86-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (1Z)-1,2-bis(butylsulfanyl)-1-hexene
• 英文别名: (Z)-1,2-bis(butylsulfanyl)hex-1-ene
• CAS: 1032738-86-5
• 化学式: C₁₄H₂₈S₂
• 分子量: 260.508
• InChiKey: NESWRHGCJOVBAM-YPKPFQOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  16
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  二丁基二硫 、 1-己炔 在 tris-(dibenzylideneacetone)dipalladium(0) 、 苯基二环己基膦 作用下， 反应 6.0h， 以85%的产率得到(1Z)-1,2-bis(butylsulfanyl)-1-hexene
  参考文献：
  名称：

  Ni和Pd催化的双炔化和末端炔烃的双硒代化中的显着配体效应：解决了立体选择性二烷基二卤化碳加成到C三化学键C键的问题。

  摘要：

  我们已经开发了两个基于Ni和Pd配合物的新催化系统，以解决二炔二卤化物（Alk2E2; E = S，Se）加成炔烃这一具有挑战性的问题。对两种催化剂体系Ni / PMe2Ph和Pd / PCy2Ph的比较研究表明，Ni催化剂在高催化活性方面优于Pd体系，具有更广泛的适用范围。开发了一种新颖的合成方法，用于从末端炔烃中以优异的立体选择性和高收率制备（Z）-双（烷硫基）烯烃和（Z）-双（烷基硒基）烯烃。

  DOI：

  10.1002/chem.200701278

文献信息

• Remarkable Ligand Effect in Ni- and Pd-Catalyzed Bisthiolation and Bisselenation of Terminal Alkynes: Solving the Problem of Stereoselective Dialkyldichalcogenide Addition to the CC Bond
  作者：Valentine P. Ananikov、Konstantin A. Gayduk、Irina P. Beletskaya、Victor N. Khrustalev、Mikhail Yu. Antipin

  DOI：10.1002/chem.200701278

  日期：2008.3.7

  We have developed two new catalytic systems based on Ni and Pd complexes to solve the challenging problem of dialkyldichalcogenide (Alk2E2; E=S, Se) addition to alkynes. A comparative study of two catalytic systems-Ni/PMe2Ph and Pd/PCy2Ph-has revealed that the Ni catalyst is superior with respect to high catalytic activity and more general scope relative to the Pd system. A novel synthetic methodology

  我们已经开发了两个基于Ni和Pd配合物的新催化系统，以解决二炔二卤化物（Alk2E2; E = S，Se）加成炔烃这一具有挑战性的问题。对两种催化剂体系Ni / PMe2Ph和Pd / PCy2Ph的比较研究表明，Ni催化剂在高催化活性方面优于Pd体系，具有更广泛的适用范围。开发了一种新颖的合成方法，用于从末端炔烃中以优异的立体选择性和高收率制备（Z）-双（烷硫基）烯烃和（Z）-双（烷基硒基）烯烃。
• Sulfur-containing alkenes—A new class of chelating ligands: Synthesis, coordination to palladium, and structure of the resulting complexes
  作者：V. P. Ananikov、A. O. Piroyan、K. A. Gaiduk、I. P. Beletskaya、V. N. Khrustalev、M. Yu. Antipin

  DOI：10.1134/s107042800912001x

  日期：2009.12

  Stable 1,2-disulfanylalkene palladium complexes [(RS-CH=CR'-SR)PdCl2] were synthesized in 85-94% yield by reaction of palladium(II) chloride with sulfur-containing ligands RS-CH=C(R')-SR (analogs of dithiolate ligands). The structure of the complexes was studied by NMR spectroscopy and quantum-chemical methods. The binding energy in palladium complexes with bis(arylsulfanyl)- and bis(alkylsulfanyl)alkenes was estimated (DFT) at 50 and 56 kcal/mol, respectively. Variation of substituents on the sulfur atoms is a convenient tool for fine tuning of the ligand properties and controlling the strength of the complex. The bite angle of the ligands does not depend on the substituent nature and is 88-89 degrees, which is typical of square-planar complexes. According to the bite angle, the examined ligands are analogs of well known bidentate phosphine ligands, but the former are more labile since the corresponding binding energy is lower by 36 kcal/mol.