(Z)-2,4-dicyclohexyl-1-(trimethylstannyl)-but-1-en-3-yne | 1415228-11-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: (Z)-2,4-dicyclohexyl-1-(trimethylstannyl)-but-1-en-3-yne
• 英文别名: (E)-2,4-dicyclohexyl-1-(trimethylstannyl)-but-1-en-3-yne
• CAS: 1415228-11-3
• 化学式: C₁₉H₃₂Sn
• 分子量: 379.173
• InChiKey: AQMDEBPJDQCSLD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.95
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  环己基乙炔 、 2-(三甲基甲锡烷基)吡啶 在 [(pentamethylcyclopentadienyl)2La(hydrido)]2 作用下， 以 氘代苯 、 氘代甲苯 为溶剂， 反应 12.0h， 生成 (Z)-2,4-dicyclohexyl-1-(trimethylstannyl)-but-1-en-3-yne
  参考文献：
  名称：

  Carbostannolysis Mediated by Bis(pentamethylcyclopentadienyl)lanthanide Catalysts. Utility in Accessing Organotin Synthons

  摘要：

  Facile carbon tin bond activation in the reaction of 2-(trimethylstannyl)pyridine (1) with the organolanthanide complexes Cp-2*LaCH(TMS)(2) (2a) and [Cp-2*LaH](2) (2b) yields Cp-2*La(2-pyridyl) (3), as well as Me3SnCH(TMS)(2) and Me3SnH, respectively. At room temperature, ethylene then undergoes insertion into the resulting La C(pyridyl) bond followed by carbostannolysis to catalytically generate 2-(2-(Me3Sn)ethyl)pyridine (4) or, with extended reaction times, 6-ethyl-2-(2(trimethylstannyl)ethyl)pyridine (5). In contrast to 1, 6-methyl-2(trimethylstannyl)pyridine (6) is unreactive, likely reflecting steric constraints. With terminal alkynes, this catalytic heterocycle-SnMe3 activation/carbostannylation process affords tin-functionalized conjugated enynes. Thus, at 60 degrees C 2b catalyzes the conversion 1 + 1-hexyne to yield (E)-2-butyl-1-(Me3Sn)-oct-1-en-3-yne in a 60:1 ratio E:Z isomer ratio. This reaction is available to alpha-monosubstituted and alpha-disubstituted terminal alkynes, while alpha-trisubstituted alkynes are too hindered for reaction. The catalytic cycle is proposed to proceed via a spectroscopically detectable Me3Sn-alkynyl intermediate which undergoes insertion into a Cp-2*La-alkynyl bond to produce the conjugated alkynyl product, which is subsequently protonolyzed from the 2-La center by a new terminal alkyne substrate molecule. NMR spectroscopic and kinetic data support the proposed pathway and indicate turnover-limiting alkyne insertion.

  DOI：

  10.1021/om301031e