(1S,2R,4S,5R)-3,3-Di-tert-butyl-3-sila-tricyclo[3.2.1.0^2,4]octane | 442525-80-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2R,4S,5R)-3,3-Di-tert-butyl-3-sila-tricyclo[3.2.1.0^2,4]octane
• 英文别名: (1R,2S,4R,5S)-3,3-ditert-butyl-3-silatricyclo[3.2.1.02,4]octane
• CAS: 442525-80-6
• 化学式: C₁₅H₂₈Si
• 分子量: 236.473
• InChiKey: LXNXJAVHFAAEIW-FNFFVJSTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.22
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  3.0
• 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：

  N-methyl-N-benzylformamide 、 (1S,2R,4S,5R)-3,3-Di-tert-butyl-3-sila-tricyclo[3.2.1.0^2,4]octane 在 copper(l) iodide 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 生成 Benzyl-((1S,2R,6R,7R)-3,3-di-tert-butyl-4-oxa-3-sila-tricyclo[5.2.1.0^2,6]dec-5-yl)-methyl-amine
  参考文献：
  名称：

  Diastereoselective Silacyclopropanations of Functionalized Chiral Alkenes

  摘要：

  Lithium reduction of di-tert-butyldichlorosilane and thermal silylene transfer (105-125 degrees C) are complementary methods for the highly diastereoselective silacyclopropanations of a range of functionalized chiral olefins to afford complex silacycles. We have shown that functionalized cyclohexenes, cyclopentenes, norbornenes, and 1,1-disubstituted alkenes undergo silacyclopropanation with excellent diastereoselectivity (92:8 to >99:1). Our results demonstrate that steric interactions, rather than oxygen-directing effects, control the approach of the silylene or silylenoid intermediate to the olefin. We believe that the sterically demanding nature of the di-tert-butylsilylene species prevents coordination to the oxygen functionality. Thermal silylene transfer conditions exhibit broad functional group tolerance; the elevated temperatures for silylene transfer, however, cannot be employed for the silacyclopropanation of substituted cyclohexenes and 1,1-disubstituted alkenes. Elaboration of the resulting functionalized silacyclopropanes provides an efficient route to polyoxygenated products.

  DOI：

  10.1021/ja020183k
• 作为产物：
  描述：

  二叔丁基氯硅烷 在 lithium 作用下， 以 四氢呋喃 、 正己烷 、 氘代苯 为溶剂， 反应 64.0h， 生成 (1S,2R,4S,5R)-3,3-Di-tert-butyl-3-sila-tricyclo[3.2.1.0^2,4]octane
  参考文献：
  名称：

  Diastereoselective Silacyclopropanations of Functionalized Chiral Alkenes

  摘要：

  Lithium reduction of di-tert-butyldichlorosilane and thermal silylene transfer (105-125 degrees C) are complementary methods for the highly diastereoselective silacyclopropanations of a range of functionalized chiral olefins to afford complex silacycles. We have shown that functionalized cyclohexenes, cyclopentenes, norbornenes, and 1,1-disubstituted alkenes undergo silacyclopropanation with excellent diastereoselectivity (92:8 to >99:1). Our results demonstrate that steric interactions, rather than oxygen-directing effects, control the approach of the silylene or silylenoid intermediate to the olefin. We believe that the sterically demanding nature of the di-tert-butylsilylene species prevents coordination to the oxygen functionality. Thermal silylene transfer conditions exhibit broad functional group tolerance; the elevated temperatures for silylene transfer, however, cannot be employed for the silacyclopropanation of substituted cyclohexenes and 1,1-disubstituted alkenes. Elaboration of the resulting functionalized silacyclopropanes provides an efficient route to polyoxygenated products.

  DOI：

  10.1021/ja020183k

文献信息

• 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。