(E)-1-(3-(trimethylsilyl)prop-1-en-1-yl)naphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (E)-1-(3-(trimethylsilyl)prop-1-en-1-yl)naphthalene
• 英文别名: trimethyl-[(E)-3-naphthalen-1-ylprop-2-enyl]silane
• 化学式: C₁₆H₂₀Si
• 分子量: 240.42
• InChiKey: NVKZRLDNNBQFBF-YRNVUSSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.19
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  (E)-1-(3,4-dihydro-1-naphthyl)-3-trimethylsilyl-2-propen-1-ol 在 4-二甲氨基吡啶 、 palladium diacetate 、 三乙胺 、 三苯基膦 、 cesium fluoride 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 14.0h， 生成 (E)-1-(3-(trimethylsilyl)prop-1-en-1-yl)naphthalene
  参考文献：
  名称：

  通过硅上取代基的1,2-转移进行的γ-硅烷化乙酸烯丙酯的钯催化反应

  摘要：

  在CsF存在下，钯催化的γ-甲硅烷基化的乙酸烯丙酯与水的反应会导致硅上取代基发生前所未有的1,2-移位，从而原位生成烯丙基硅烷。当使用具有氟化取代基的贫电子膦配体时，钯的催化活性增加。对该反应的进一步研究表明，基团从硅的迁移能力的近似顺序为：PhC≡C，烯丙基> Bn> Ph，乙烯基>烷基（Me，Et）。利用密度泛函理论研究了反应机理。最后，还研究了Hosomi-Sakurai型醛与原位生成的α，γ-二取代烯丙基硅烷的烯丙基化反应。

  DOI：

  10.1016/j.tet.2020.131493

文献信息

• Silylation of Allylic Trifluoroacetates and Acetates Using Organodisilanes Catalyzed by Palladium Complex
  作者：Yasushi Tsuji、Masahiro Funato、Masakatsu Ozawa、Hiroaki Ogiyama、Satoshi Kajita、Takashi Kawamura

  DOI：10.1021/jo960345t

  日期：1996.1.1

  Silylation of allylic acetates (1) using organodisilanes (2) was carried out in the presence of a catalytic amount of Pd(DBA)2-LiCl at 100 degrees C. The silylation proceeded smoothly without beta-hydrogen elimination of. resulting (pi-allyl)palladium intermediate. The added chloride salt such as LiCl or NaCl was indispensable for the catalytic activity. On the other hand, remarkable improvement of the silylation was realized by employing allylic trifluoroacetates (4) in place of the acetates (1) as the substrates. The silylation proceeded even at room temperature, and the added chloride salts was not necessary as the catalyst component. In the silylation, transmetalation of the disilanes (2) with (eta(3)-allyl)palladium intermediate (7) might be a critical step in the catalytic cycle. Model reactions for the transmetalation were carried out.
• Palladium-catalyzed silylation of allylic acetates with hexamethyldisilane or (trimethylsilyl)tributylstannane
  作者：Yasushi Tsuji、Satoshi Kajita、Shinya Isobe、Masahiro Funato

  DOI：10.1021/jo00066a005

  日期：1993.7

  Various allylic acetates (1a-j) are silylated with hexamethyldisilane (Me3SiSiMe3, 2) in the presence of a catalytic amount of Pd(DBA)2 and LiCl at 100-degrees-C to afford the corresponding allylic silanes in high yields. In addition, (trimethylsilyl)tributylstannane (Me3SiSnBu3, 3) can be used for the silylation of aromatic allylic acetates 1g-j at room temperature.
• Highly Regioselective Palladium-Catalyzed Internal Arylation of Allyltrimethylsilane with Aryl Triflates
  作者：Kristofer Olofsson、Mats Larhed、Anders Hallberg

  DOI：10.1021/jo980249n

  日期：1998.7.1

  Highly regioselective ligand-controlled Heck-arylation reactions of allyltrimethylsilane, delivering branched beta-products, were performed in moderate to good yields. The high preference for internal over terminal double-bond arylation suggests a contribution from the beta-cation-stabilizing effect of silicon. Microwave-promoted palladium-catalyzed coupling reactions proceeded with the same regioselectivity in six entries out of eight with the reaction times cut sharply down to 5-10 min.
• Tsuji Yasushi, Kajita Satoshi, Isobe Shinya, Funato Masahiro, J. Org. Chem., 58 (1993) N 14, S 3607-3608
  作者：Tsuji Yasushi, Kajita Satoshi, Isobe Shinya, Funato Masahiro

  DOI：——

  日期：——
• Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon
  作者：Yoshikazu Horino、Mayo Ishibashi、Kosuke Nakasai、Toshinobu Korenaga

  DOI：10.1016/j.tet.2020.131493

  日期：2020.10

  The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate

  在CsF存在下，钯催化的γ-甲硅烷基化的乙酸烯丙酯与水的反应会导致硅上取代基发生前所未有的1,2-移位，从而原位生成烯丙基硅烷。当使用具有氟化取代基的贫电子膦配体时，钯的催化活性增加。对该反应的进一步研究表明，基团从硅的迁移能力的近似顺序为：PhC≡C，烯丙基> Bn> Ph，乙烯基>烷基（Me，Et）。利用密度泛函理论研究了反应机理。最后，还研究了Hosomi-Sakurai型醛与原位生成的α，γ-二取代烯丙基硅烷的烯丙基化反应。