1,1-di-tert-butyl-2,2-dimethylsilirane | 172220-55-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1,1-di-tert-butyl-2,2-dimethylsilirane
• 英文别名: 2,2-dimethyl-di-tertbutylsilacyclopropane；di-tert-butyl-2,2-dimethylsilirane；1,1-Ditert-butyl-2,2-dimethylsilirane
• CAS: 172220-55-2
• 化学式: C₁₂H₂₆Si
• 分子量: 198.424
• InChiKey: XRIZRYSQFSYDOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  13
• 可旋转键数：
  2
• 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：

  allyl 2-oxo-2-phenylacetate 、 1,1-di-tert-butyl-2,2-dimethylsilirane 在 silver(I) tosylate 作用下， 以 甲苯 为溶剂， 以80%的产率得到2,2-Ditert-butyl-5-phenyl-5-prop-2-enyl-1,3,2-dioxasilolan-4-one
  参考文献：
  名称：

  Synthesis of Tertiary α-Hydroxy Acids by Silylene Transfer to α-Keto Esters

  摘要：

  alpha-Keto esters can be converted into alpha-hydroxy acids in a single flask involving metal-catalyzed silylene transfer, 6 pi-electrocyclization, Ireland-Claisen rearrangement, and hydrolysis. This reaction sequence is stereoselective and tolerates alkyl- and aryl-substituted a-keto ester substrates as well as an alpha-imino ester.

  DOI：

  10.1021/ol702148x
• 作为产物：
  描述：

  二叔丁基氯硅烷 、 异丁烯 在 lithium 作用下， 以 四氢呋喃 为溶剂， 以50%的产率得到1,1-di-tert-butyl-2,2-dimethylsilirane
  参考文献：
  名称：

  Synthesis of Tertiary α-Hydroxy Acids by Silylene Transfer to α-Keto Esters

  摘要：

  alpha-Keto esters can be converted into alpha-hydroxy acids in a single flask involving metal-catalyzed silylene transfer, 6 pi-electrocyclization, Ireland-Claisen rearrangement, and hydrolysis. This reaction sequence is stereoselective and tolerates alkyl- and aryl-substituted a-keto ester substrates as well as an alpha-imino ester.

  DOI：

  10.1021/ol702148x
• 作为试剂：
  描述：

  (S,E)-1-(tert-butyldimethylsilyloxy)-5-(4-methoxybenzyloxy)pent-3-en-2-yl 2-oxopropanoate 在 1,1-di-tert-butyl-2,2-dimethylsilirane 、 silver(I) 4-methylbenzenesulfonate 作用下， 以 甲苯 为溶剂， 反应 3.5h， 以80%的产率得到(2R,3R,E)-6-(tert-butyldimethylsilyloxy)-2-hydroxy-3-((4-methoxybenzyloxy)methyl)-2-methylhex-4-enoic acid
  参考文献：
  名称：

  Silylene transfer to α-keto esters and application to the synthesis of γ-lactones

  摘要：

  Disubstituted alpha-hydroxy acids have been synthesized by metal-catalyzed silylene transfer to alpha-keto esters. A range of substituents are tolerated in the transformation with the exception of branched groups at the vinylic position. The alpha-hydroxy acid products can be converted into gamma-lactones using a variety of lactonization conditions. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.05.066

文献信息

• Metal-Catalyzed Rearrangement of Homoallylic Ethers to Silylmethyl Allylic Silanes in the Presence of a Di-<i>tert</i>-butylsilylene Source
  作者：Pamela A. Cleary、K. A. Woerpel

  DOI：10.1021/ol052456x

  日期：2005.11.1

  transfer to gem-disubstituted alkenes to form silacyclopropanes, we discovered an unprecedented reaction of homoallylic ethers. When silylene transfer was performed at room temperature or above, two di-tert-butylsilylene units were incorporated into the molecule, and complete rearrangement of the carbon backbone occurred. This report describes the scope of this unique reaction as well as the mechanistic

  [反应：见正文]在研究将二叔丁基亚甲硅烷基转移到宝石二取代的烯烃以形成硅环丙烷的范围时，我们发现了均空醚的空前反应。当在室温或更高温度下进行亚甲硅烷基转移时，两个二叔丁基亚甲硅烷基单元被引入分子中，并且碳主链发生了完全重排。该报告描述了这种独特反应的范围以及进行了机制研究的机制。
• 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。
• 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.
• Synthesis of Tertiary α-Hydroxy Acids by Silylene Transfer to α-Keto Esters
  作者：Brett E. Howard、K. A. Woerpel

  DOI：10.1021/ol702148x

  日期：2007.10.1

  alpha-Keto esters can be converted into alpha-hydroxy acids in a single flask involving metal-catalyzed silylene transfer, 6 pi-electrocyclization, Ireland-Claisen rearrangement, and hydrolysis. This reaction sequence is stereoselective and tolerates alkyl- and aryl-substituted a-keto ester substrates as well as an alpha-imino ester.