2-butyl-1,1-di-tert-butylsilacyclopropane | 171974-57-5

• 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: 2-butyl-1,1-di-tert-butylsilacyclopropane
• 英文别名: 2-Butyl-1,1-ditert-butylsilirane
• CAS: 171974-57-5
• 化学式: C₁₄H₃₀Si
• 分子量: 226.478
• InChiKey: XHTJCRDKQVBBMC-UHFFFAOYSA-N

物化性质

• 沸点：
  257.1±9.0 °C(Predicted)
• 密度：
  0.81±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  2-butyl-1,1-di-tert-butylsilacyclopropane 在 叔丁基过氧化氢 、 18-冠醚-6 、 potassium tert-butylate 、 四丁基氟化铵 、 potassium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.0h， 生成 syn-2-butyl-1-phenylpropane-1,3-diol
  参考文献：
  名称：

  Stereo- and Regioselectivity of Reactions of Siliranes with Aldehydes and Related Substrates

  摘要：

  Siliranes undergo stereoselective and regioselective insertions of benzaldehyde to provide oxasi-lacyclopentane products. The thermal reaction (>100 degrees C) leads to more decomposition and side products, whereas the catalyzed variant (t-BuOK, (25 degrees C) proceeds more cleanly with a high degree of inversion (>95%). Treatment of siliranes with enolizable aldehydes leads to silyl enol ethers. The reaction of a silirane at high temperatures with an imine leads to reductive dimerization, presumably by way of intermediate-free silylene. The mechanism for the catalyzed insertion of benzaldehyde is discussed.

  DOI：

  10.1021/jo970263k
• 作为产物：
  描述：

  1-己烯 、 二叔丁基氯硅烷 在 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以86%的产率得到2-butyl-1,1-di-tert-butylsilacyclopropane
  参考文献：
  名称：

  Stereo- and Regioselectivity of Reactions of Siliranes with Aldehydes and Related Substrates

  摘要：

  Siliranes undergo stereoselective and regioselective insertions of benzaldehyde to provide oxasi-lacyclopentane products. The thermal reaction (>100 degrees C) leads to more decomposition and side products, whereas the catalyzed variant (t-BuOK, (25 degrees C) proceeds more cleanly with a high degree of inversion (>95%). Treatment of siliranes with enolizable aldehydes leads to silyl enol ethers. The reaction of a silirane at high temperatures with an imine leads to reductive dimerization, presumably by way of intermediate-free silylene. The mechanism for the catalyzed insertion of benzaldehyde is discussed.

  DOI：

  10.1021/jo970263k

文献信息

• Stereospecific and Regioselective Reactions of Silacyclopropanes with Carbonyl Compounds Catalyzed by Copper Salts:  Evidence for a Transmetalation Mechanism
  作者：Annaliese K. Franz、K. A. Woerpel

  DOI：10.1021/ja982897u

  日期：1999.2.1

  demonstrated that formamides reacted faster than enals, which reacted faster than enoates; saturated aldehydes did not undergo insertion. With a cis-disubstituted silacyclopropane, products of silylene transfer were observed. The stereochemistry, regiochemistry, and chemoselectivity of carbonyl insertion as well as the silylene transfer processes can be explained by a mechanism involving transmetalation

  硅环丙烷与羰基化合物在温和条件下（10 mol% 金属盐，e22 °C）以立体定向和高度立体选择性、区域选择性和化学选择性的方式反应。在大多数情况下，CuI 或 CuBr2 是最佳催化剂，尽管 ZnBr2 在一些例子中表现得相当好。插入发生时保留构型，并且在 enal 和甲酰胺的情况下，在新形成的立体中心具有高非对映选择性。对于不对称底物，插入发生在具有完全区域选择性的更多取代的碳-硅键上。竞争实验表明，甲酰胺反应比 enal 快，而 enal 反应比 enoate 快；饱和醛没有进行插入。对于顺式二取代的硅杂环丙烷，观察到亚甲硅烷基转移产物。立体化学，
• 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。
• ZnBr2-Catalyzed Insertions of Carbonyl Compounds into Silacyclopropanes: Regiochemical Reversal Dependent on Metal Salt
  作者：Annaliese K. Franz、K. A. Woerpel

  DOI：10.1002/1521-3773(20001201)39:23<4295::aid-anie4295>3.0.co;2-a

  日期：2000.12.1
• 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.