1-Phenyl-3-(trimethylsilyl)-4-penten-1-yne | 34602-23-8

• 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: 1-Phenyl-3-(trimethylsilyl)-4-penten-1-yne
• 英文别名: Trimethyl(5-phenylpent-1-en-4-yn-3-yl)silane
• CAS: 34602-23-8
• 化学式: C₁₄H₁₈Si
• 分子量: 214.382
• InChiKey: OGHNPPMLWBKUTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  苯基乙炔三丁基锡 、 (1-溴-2-丙烯-1-基)(三甲基)硅烷 在 bis(acetylacetonate)nickel(II) 、 二异丁基氢化铝 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 1-Phenyl-3-(trimethylsilyl)-4-penten-1-yne 、 1-Phenyl-5-(trimethylsilyl)-4-penten-1-yne
  参考文献：
  名称：

  Nickel-catalyzed cross-coupling reaction of allyl halides with alkynyltins

  摘要：

  A cross-coupling reaction of allyl halides 1 with alkynyltins 3 in the presence of ''Ni(PR(3))(n)'' (R = Ph, Oft, or OPh) catalyst was carried out in THF at reflux to give 1,4-enynes, The regioselectivity of the coupling of 1f-i with 3a was investigated in the presence of various phosphorus ligands. Interestingly, prenyl (1j) and geranyl chlorides (1k) selectively reacted with 3 at the more-hindered positions of substituted eta(3)-allylnickel intermediates 21 (M = Ni) to yield 23 and 25, respectively. Regioselectivity in these reactions may result from greater steric crowding between the phosphorus ligand and the disubstituted position in 26b than in 26a. In contrast, the palladium-catalyzed reactions of 1j and 1k with 3 selectively gave 22 and 24, respectively. Thus, the steric crowding in a Pd analogue of 26b is less than that in a Ni analogue of 26b, since Pd has a larger covalent radius than Ni.

  DOI：

  10.1021/jo00123a006

文献信息

• Nickel-catalyzed cross-coupling reaction of allyl halides with alkynyltins
  作者：Dong-Mei Cui、Naoko Hashimoto、Shin-ichi Ikeda、Yoshiro Sato

  DOI：10.1021/jo00123a006

  日期：1995.9

  A cross-coupling reaction of allyl halides 1 with alkynyltins 3 in the presence of ''Ni(PR(3))(n)'' (R = Ph, Oft, or OPh) catalyst was carried out in THF at reflux to give 1,4-enynes, The regioselectivity of the coupling of 1f-i with 3a was investigated in the presence of various phosphorus ligands. Interestingly, prenyl (1j) and geranyl chlorides (1k) selectively reacted with 3 at the more-hindered positions of substituted eta(3)-allylnickel intermediates 21 (M = Ni) to yield 23 and 25, respectively. Regioselectivity in these reactions may result from greater steric crowding between the phosphorus ligand and the disubstituted position in 26b than in 26a. In contrast, the palladium-catalyzed reactions of 1j and 1k with 3 selectively gave 22 and 24, respectively. Thus, the steric crowding in a Pd analogue of 26b is less than that in a Ni analogue of 26b, since Pd has a larger covalent radius than Ni.