benzyl di-tert-butylsilacyclopropane | 178394-33-7

• 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: benzyl di-tert-butylsilacyclopropane
• 英文别名: 2-Benzyl-1,1-ditert-butylsilirane；2-benzyl-1,1-ditert-butylsilirane
• CAS: 178394-33-7
• 化学式: C₁₇H₂₈Si
• 分子量: 260.495
• InChiKey: XIVMDWBQCJEKOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.66
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  甲酸甲酯 、 benzyl di-tert-butylsilacyclopropane 在 zinc dibromide 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (S)-3-Benzyl-2,2-di-tert-butyl-5-methoxy-[1,2]oxasilolane 、
  参考文献：
  名称：

  Metal-Catalyzed Silacyclopropanation of Mono- and Disubstituted Alkenes

  摘要：

  As an alternative to the strongly reducing conditions necessary for the formation of silacyclopropanes, silylene transfer was developed as a mild, functional group tolerant method of silacyclopropanation. Complex silacyclopropanes were formed from functionalized alkenes using cyclohexane di-tert-butyl silacyclopropane, 1, as the source of t-Bu(2)Si. Di-tert-butyl silylene can be generated from 1 through the use of a catalytic amount of a metal salt. At -27 degrees C, silver triflate catalyzes the transfer of t-Bu(2)Si from 1 to mono- and disubstituted alkenes stereospecifically and diastereoselectively. In situ functionalization of silacyclopropanes with catalytic zinc bromide and methyl formate provides for an expedient one-flask synthesis of complex oxasilacyclopentanes from alkenes.

  DOI：

  10.1021/ja020566i
• 作为产物：
  描述：

  烯丙苯 、 di-tert-butylsilylene 生成 benzyl di-tert-butylsilacyclopropane
  参考文献：
  名称：

  Siliranes：形成，异腈插入和热重排

  摘要：

  的siliranes 7-10和22以及所述vinylsiliranes 14-16，20和21是由亚甲硅烷基的[1 + 2] -cycloadditions制备2与烯烃和二烯。合成了第一个异腈插入产物，即硅杂环丁胺26-28，并通过X射线晶体学确定了28的结构。经热解后，20-22进行了定量重排，得到了29-32的化合物。

  DOI：

  10.1016/0040-4039(96)00650-8

文献信息

• Mechanism of Silver-Mediated Di-<i>tert</i>-butylsilylene Transfer from a Silacyclopropane to an Alkene
  作者：Tom G. Driver、K. A. Woerpel

  DOI：10.1021/ja0306563

  日期：2004.8.1

  cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P)2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic

  环己烯硅杂环丙烷 1 和单取代烯烃在 5 mol% (Ph3P)2AgOTf 存在下的反应动力学研究表明银介导的二叔丁基亚甲硅烷基转移的可能机制。环己烯硅杂环丙烷 1 的动力学顺序被确定为 1。在单取代烯烃和环己烯浓度中观察到反向动力学饱和行为（速率抑制）。观察到催化剂浓度的饱和动力学行为。使用低温 29Si NMR 光谱观察到反应性中间体，即甲硅烷基银络合物。取代苯乙烯和不足量 1 之间的竞争实验与哈米特方程很好地相关，并使用 sigmap 常数提供了 -0.62 +/- 0.02 的 rho 值。
• Mechanism of Di-<i>tert</i>-Butylsilylene Transfer from a Silacyclopropane to an Alkene
  作者：Tom G. Driver、K. A. Woerpel

  DOI：10.1021/ja0301370

  日期：2003.9.1

  Kinetic and thermodynamic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes suggested a possible mechanism for di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 and cyclohexene were determined to be 1 and -1, respectively. Saturation kinetic behavior in monosubstituted alkene concentration was observed. Competition experiments between

  环己烯硅杂环丙烷 1 和单取代烯烃反应的动力学和热力学研究表明了二叔丁基亚甲硅烷基转移的可能机制。环己烯硅杂环丙烷 1 和环己烯的动力学顺序分别确定为 1 和 -1。观察到单取代烯烃浓度下的饱和动力学行为。取代的苯乙烯和 1 的不足量的二叔丁基亚甲硅烷之间的竞争实验与哈米特方程很好地相关，并使用 sigma(p) 常数提供了 -0.666 +/- 0.008 的 rho 值。这些数据支持两步机制，包括从 1 中可逆地挤出二叔丁基亚甲硅烷，然后是亚甲硅烷对单取代烯烃的不可逆协同亲电攻击。发现 Eyring 激活参数为 DeltaH++ = 22.1 +/- 0.9 kcal.mol(-1) 和 DeltaS++ = -15 +/- 2 eu。环烯烃和烯丙苯之间的竞争实验确定环烯烃是更有效的亚甲硅烷陷阱 (k(rel) =1.3，DeltaDeltaG++ = 0.200 kcal.mol(-
• Metal-Catalyzed Di-<i>tert-</i>butylsilylene Transfer:  Synthesis and Reactivity of Silacyclopropanes
  作者：Jelena Ćiraković、Tom G. Driver、K. A. Woerpel

  DOI：10.1021/jo0355505

  日期：2004.6.1

  developed as a mild, operationally simple, functional-group-tolerant method for silacyclopropane formation. Di-tert-butylsilylene was transferred from cyclohexene silacyclopropane 1 to an alkene through the use of a metal salt. Silacyclopropanation occurred at temperatures as low as −27 °C when AgOTf or AgOC(O)CF3 were used as catalysts. Complex silacyclopropanes were formed stereospecifically and

  金属催化的二叔丁基亚甲硅烷基转移反应是一种温和的，操作简便的，官能团耐受的硅环丙烷形成方法。通过使用金属盐将二叔丁基亚甲硅烷基从环己烯硅环丙烷1转移至烯烃。当将AgOTf或AgOC（O）CF 3用作催化剂时，硅环丙烷化发生在低至-27°C的温度下。复杂的硅杂环丙烷是由官能化烯烃立体定向和非对映选择性地形成的。在整个过程中，硅环丙烷与各种羰基化合物（包括醛，酮，甲酸酯和甲酰胺）反应，可以有效地将烯烃转化为具有定义立体化学的氧杂硅环戊烷。
• Siliranes: Formation, isonitrile insertions, and thermal rearrangements
  作者：Edwin Kroke、Stefan Willms、Manfred Weidenbruch、Wolfgang Saak、Siegfried Pohl、Heinrich Marsmann

  DOI：10.1016/0040-4039(96)00650-8

  日期：1996.5

  alkenes and dienes. The first isonitrile insertion products, the silacyclobutanimines 26–28 were synthesized and the structure of 28 was determined by X-ray crystallography. Upon thermolysis 20–22 rearranged quantitatively to furnish the compounds 29–32.

  的siliranes 7-10和22以及所述vinylsiliranes 14-16，20和21是由亚甲硅烷基的[1 + 2] -cycloadditions制备2与烯烃和二烯。合成了第一个异腈插入产物，即硅杂环丁胺26-28，并通过X射线晶体学确定了28的结构。经热解后，20-22进行了定量重排，得到了29-32的化合物。
• Metal-Catalyzed Silacyclopropanation of Mono- and Disubstituted Alkenes
  作者：Jelena Ćiraković、Tom G. Driver、K. A. Woerpel

  DOI：10.1021/ja020566i

  日期：2002.8.1

  As an alternative to the strongly reducing conditions necessary for the formation of silacyclopropanes, silylene transfer was developed as a mild, functional group tolerant method of silacyclopropanation. Complex silacyclopropanes were formed from functionalized alkenes using cyclohexane di-tert-butyl silacyclopropane, 1, as the source of t-Bu(2)Si. Di-tert-butyl silylene can be generated from 1 through the use of a catalytic amount of a metal salt. At -27 degrees C, silver triflate catalyzes the transfer of t-Bu(2)Si from 1 to mono- and disubstituted alkenes stereospecifically and diastereoselectively. In situ functionalization of silacyclopropanes with catalytic zinc bromide and methyl formate provides for an expedient one-flask synthesis of complex oxasilacyclopentanes from alkenes.