(Z)-1-(triphenylsilyl)-1-dodecene | 104066-52-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z)-1-(triphenylsilyl)-1-dodecene
• 英文别名: [(Z)-dodec-1-enyl]-triphenylsilane
• CAS: 104066-52-6
• 化学式: C₃₀H₃₈Si
• 分子量: 426.717
• InChiKey: GRKKJFWMQWIUIJ-OOAXWGSJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.78
• 重原子数：
  31
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  苯甲醛 、 (Z)-1-(triphenylsilyl)-1-dodecene 在 正丁基锂 作用下， 以15%的产率得到1-Phenyl-2-((E)-2-triphenylsilanyl-vinyl)-undecan-1-ol
  参考文献：
  名称：

  1-丙烯基三苯基硅烷和1-丙烯基三苯基锗烷制备(三苯基甲硅烷基)烯丙基阴离子和(三苯基锗基)烯丙基阴离子及其与亲电子试剂的反应

  摘要：

  在 THF-HMPA 中用 n-BuLi 处理 1-丙烯基三苯基硅烷提供（三苯基甲硅烷基）烯丙基阴离子，该阴离子与衍生自 2-丙烯基三苯基硅烷和碱的阴离子相同。还描述了（三苯基锗基）烯丙基阴离子的生成。将烷基卤化物或羰基化合物加成到这些阴离子上会区域选择性地产生相应的加合物。

  DOI：

  10.1246/cl.1987.2029
• 作为产物：
  描述：

  1-十二炔 、 三苯基硅烷 在 二氯乙基铝 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以40%的产率得到(Z)-1-(triphenylsilyl)-1-dodecene
  参考文献：
  名称：

  Lewis Acid Catalyzed Highly Regio- and Stereocontrolled Trans-Hydrosilylation of Alkynes and Allenes

  摘要：

  Lewis acids such as AlCl3 or EtAlCl2 dramatically catalyzed the hydrosilylation of alkynes 1 with trialkylsilanes to produce the corresponding cis-vinylsilanes 2 in a regio- and trans-stereoselective manner. For example, the hydrosilylation of 1-dodecyne la with triethylsilane in the presence of 0.2 equiv of AlCl3 gave cis-1-(triethylsilyl)-1-dodecene in 93% yield. Other alkyl- and phenyl-substituted terminal and internal acetylenes also underwent trans-hydrosilylation very smoothly. In the case of alkoxy- or silyloxy-substituted acetylenes, the use of 1.2 equiv of AlCl3 or EtAlCl2 was essential to obtain the corresponding trans-hydrosilylation products in high yields. Moreover, AlCl3 catalyzed the hydrosilylation of aromatic allenes 11, producing the alkenylsilanes 12 with high regio- and stereoselectivities in moderate to high chemical yields. Not only the simple monosubstituted, but also the disubstituted and trisubstituted allenes, underwent the hydrosilylation reaction smoothly, serving as a useful tool for the synthesis of differently substituted vinylsilanes which are not easily available through the previously known methodologies. The mechanisms for these catalytic reactions of alkynes and allenes are proposed.

  DOI：

  10.1021/jo9824293

文献信息

• Triethylborane Induced Stereoselective Radical Addition of R₃SiH to Acetylenes and Stereoselective Reduction of Alkenyl Iodides with Tris(trimethylsilyl)silane
  作者：Katsukiyo Miura、Koichiro Oshima、Kiitiro Utimoto

  DOI：10.1246/bcsj.66.2356

  日期：1993.8

  Triethylborane induced radical addition of various organosilanes (R3SiH) to acetylenes has been studied. Among them, tris(trimethylsilyl)silane (TTMSS) proved to be the best reagent for the hydrosilylation of acetylenic compounds in terms of yield and stereoselectivity. For instance, reaction of 1-dodecyne with TTMSS at room temperature for 3 h under Et3B catalyst provided (Z)-1-tris(trimethylsilyl)silyl-1-dodecene

  已经研究了三乙基硼烷引发的各种有机硅烷 (R3SiH) 与乙炔的自由基加成。其中，就产率和立体选择性而言，三（三甲基甲硅烷基）硅烷（TTMSS）被证明是炔类化合物氢化硅烷化的最佳试剂。例如，1-十二炔与 TTMSS 在室温下在 Et3B 催化剂下反应 3 小时，选择性地提供了 (Z)-1-三(三甲基甲硅烷基)甲硅烷基-1-十二烯，产率为 98%。已经研究了用 TTMSS-Et3B 或 n-Bu3SnH-Et3B 还原烯基碘的立体化学过程。在室温下用 TTMSS-Et3B 处理 1-二甲基苯基甲硅烷基-2-碘-1-十二烯，选择性地提供 (Z)-1-二甲基苯基甲硅烷基-1-十二烯 (Z/E > 30/1)。另一方面，用 n-Bu3SnH-Et3B 处理只得到 (E)-1-二甲基苯基甲硅烷基-1-十二烯。
• Lewis Acid-Catalyzed <i>trans</i>-Hydrosilylation of Alkynes
  作者：Naoki Asao、Tomoko Sudo、Yoshinori Yamamoto

  DOI：10.1021/jo961508g

  日期：1996.1.1
• Lewis Acid Catalyzed Highly Regio- and Stereocontrolled <i>Trans</i>-Hydrosilylation of Alkynes and Allenes
  作者：Tomoko Sudo、Naoki Asao、Vladimir Gevorgyan、Yoshinori Yamamoto

  DOI：10.1021/jo9824293

  日期：1999.4.1

  Lewis acids such as AlCl3 or EtAlCl2 dramatically catalyzed the hydrosilylation of alkynes 1 with trialkylsilanes to produce the corresponding cis-vinylsilanes 2 in a regio- and trans-stereoselective manner. For example, the hydrosilylation of 1-dodecyne la with triethylsilane in the presence of 0.2 equiv of AlCl3 gave cis-1-(triethylsilyl)-1-dodecene in 93% yield. Other alkyl- and phenyl-substituted terminal and internal acetylenes also underwent trans-hydrosilylation very smoothly. In the case of alkoxy- or silyloxy-substituted acetylenes, the use of 1.2 equiv of AlCl3 or EtAlCl2 was essential to obtain the corresponding trans-hydrosilylation products in high yields. Moreover, AlCl3 catalyzed the hydrosilylation of aromatic allenes 11, producing the alkenylsilanes 12 with high regio- and stereoselectivities in moderate to high chemical yields. Not only the simple monosubstituted, but also the disubstituted and trisubstituted allenes, underwent the hydrosilylation reaction smoothly, serving as a useful tool for the synthesis of differently substituted vinylsilanes which are not easily available through the previously known methodologies. The mechanisms for these catalytic reactions of alkynes and allenes are proposed.
• Preparation of (Triphenylsilyl)allyl Anion and (Triphenylgermyl)allyl Anion from 1-Propenyltriphenylsilane and 1-Propenyltriphenylgermane and Their Reactions with Electrophiles
  作者：Kuni Wakamatsu、Koichiro Oshima、Kiitiro Utimoto

  DOI：10.1246/cl.1987.2029

  日期：1987.10.5

  Treatment of 1-propenyltriphenylsilane with n-BuLi in THF-HMPA provides (triphenylsilyl)allyl anion which is identical with an anion derived from 2-propenyltriphenylsilane and base. Generation of (triphenylgermyl)allyl anion is also described. Addition of alkyl halides or carbonyl compounds to these anions gives the corresponding adducts regioselectively.

  在 THF-HMPA 中用 n-BuLi 处理 1-丙烯基三苯基硅烷提供（三苯基甲硅烷基）烯丙基阴离子，该阴离子与衍生自 2-丙烯基三苯基硅烷和碱的阴离子相同。还描述了（三苯基锗基）烯丙基阴离子的生成。将烷基卤化物或羰基化合物加成到这些阴离子上会区域选择性地产生相应的加合物。