(1R,6S)-7,7-Di-tert-butyl-7-sila-bicyclo[4.1.0]heptane | 130451-35-3

• 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: (1R,6S)-7,7-Di-tert-butyl-7-sila-bicyclo[4.1.0]heptane
• 英文别名: (1S,6R)-7,7-ditert-butyl-7-silabicyclo[4.1.0]heptane
• CAS: 130451-35-3
• 化学式: C₁₄H₂₈Si
• 分子量: 224.462
• InChiKey: GPLNMQGTZICJEB-TXEJJXNPSA-N

物化性质

• 沸点：
  100-110 °C(Press: 0.05 Torr)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.36
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• 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：

  (1R,6S)-7,7-Di-tert-butyl-7-sila-bicyclo[4.1.0]heptane 在 silver trifluoroacetate 作用下， 生成 (1-(di-tert-butyl(methyl)silyl)cyclohex-2-en-1-yl)methanol
  参考文献：
  名称：

  Strained organosilacyclic compounds: synthesis of anti-Bredt olefins and trans-dioxasilacyclooctenes

  摘要：

  将硅烯插入乙烯环氧化物的烯丙基碳-氧键生成1,2-硅氧烷。这些中间体经过高度非对映选择性的反应与醛发生加成，形成反-Bredt烯和反-二氧硅烷环辛烯。对这些受到张力的反环烷烃的外侧面选择性地进行亲电试剂的加成，可以得到有价值的功能化化合物。

  DOI：

  10.1039/c003227a
• 作为产物：
  描述：

  二叔丁基氯硅烷 、 环己烯 在 lithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 48.0h， 以71%的产率得到(1R,6S)-7,7-Di-tert-butyl-7-sila-bicyclo[4.1.0]heptane
  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

• Silylene-Mediated Polarity Reversal of Dienoates: Additions of Dienoates to Aldehydes at the δ-Position To Form <i>trans</i>-Dioxasilacyclononenes
  作者：Christian C. Ventocilla、K. A. Woerpel

  DOI：10.1021/ja109631z

  日期：2011.1.26

  trans-dioxasilacyclononenes as single stereoisomers. This reaction, which converts the δ-position of the unsaturated carbonyl compound into a nucleophilic center, represents an inversion of polarity from the normal pattern of reactivity. The stereospecificity of the reaction suggests that the addition to aldehydes occurred through a closed, chairlike six-membered transition state. This reaction can be

  亚甲硅烷向 α,β,γ,δ-不饱和羰基化合物的转移产生了氧杂硅杂环戊烯，这些杂硅杂环戊烯经过与醛的热加成以产生作为单一立体异构体的反式二氧杂硅杂环壬烯。该反应将不饱和羰基化合物的 δ 位转化为亲核中心，代表了正常反应模式的极性反转。该反应的立体特异性表明醛的加成是通过一个封闭的、椅子状的六元过渡态发生的。通过使用手性助剂来控制氧硅杂环戊烯的形成，该反应可用于制备对映体纯材料。所得反式环烯烃的官能化完全立体选择性地发生。
• Diastereoselective silylene transfer reactions to chiral enantiopure alkenes: effects of ligand size and substrate bias
  作者：Christina Z. Rotsides、K. A. Woerpel

  DOI：10.1039/c6dt04612f

  日期：——

  the stereoselective construction of compounds containing carbon–silicon bonds. Despite their synthetic utility, the development of either an enantioselective or diastereoselective metal-catalyzed silylene transfer reaction, in which ligands on the metal catalyst control stereoselectivity, has not been achieved. In this article, we report that the structure of the alkene is the most important for controlling

  对于含有碳-硅键的化合物的立体选择结构，亚甲硅烷基是有用的反应性中间体。尽管它们具有合成用途，但尚未实现对映选择性或非对映选择性金属催化的甲硅烷基转移反应的发展，其中金属催化剂上的配体控制立体选择性。在本文中，我们报告了烯烃的结构对于控制这些反应中的立体选择性最重要。动力学控制的硅烷环丙烷化反应的立体化学过程不受金属上配体的性质或手性的影响。（90当亚甲硅烷基转移反应是可逆的，然而，可将产品以高度非对映选择性的形成：10 DR）。
• 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。
• Insertion Reactions of Silacyclopropanes: Evidence for a Radical-Based Mechanism
  作者：Christina Z. Rotsides、K. A. Woerpel

  DOI：10.1021/acs.organomet.6b00469

  日期：2016.9.26

  Silacyclopropanes reacted rapidly and selectively with p-benzoquinones, to provide oxasilacyclopentanes. Ring expansion products were observed in the absence of a catalyst, elevated temperatures, or irradiation. As substitution was increased on the silacyclopropane ring, improved stereoselectivity was observed. In some cases, the regiochemistry was controlled depending on the extent of stabilization of the reactive intermediates involved. A radical clock experiment, along with stereochemical studies, confirmed that radical intermediates were involved in the ring-expansion reaction. The scope of this radical reaction was expanded to include dienones, aryl aldehydes, and electron-deficient enones in addition to benzoquinones. In the case of aryl aldehydes and electron-deficient enones, the radical reaction can be used to generate silylenes from silacyclopropanes.
• Potassium fluoride activated alcoholysis of hindered siliranes
  作者：Rajkumar Kumarathasan、Philip Boudjouk

  DOI：10.1016/s0040-4039(00)94479-4

  日期：1990.1