1-(tert-butyldimethylsiloxy)-3-methyl-3-butene | 74915-94-9

• 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: 1-(tert-butyldimethylsiloxy)-3-methyl-3-butene
• 英文别名: tert-butyldimethyl((3-methylbut-3-en-1-yl)oxy)silane；tert-butyldimethyl(3-methylbut-3-enyloxy)silane；Silane, (1,1-dimethylethyl)dimethyl[(3-methyl-3-butenyl)oxy]-；tert-butyl-dimethyl-(3-methylbut-3-enoxy)silane
• CAS: 74915-94-9
• 化学式: C₁₁H₂₄OSi
• 分子量: 200.396
• InChiKey: URMSJBDSCVYIKA-UHFFFAOYSA-N

物化性质

• 沸点：
  201.6±9.0 °C(Predicted)
• 密度：
  0.810±0.06 g/cm3(Predicted)
• 保留指数：
  1084.9

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(tert-butyldimethylsiloxy)-3-methyl-3-butene 在 硼烷四氢呋喃络合物 、 sodium hydroxide 、 双氧水 作用下， 生成 4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol
  参考文献：
  名称：

  Relative Asymmetric Induction in the Intramolecular Reaction between Alkynes and Cyclopropylcarbene−Chromium Complexes:  Stereocontrolled Synthesis of Five-Membered Rings Fused to Oxygen Heterocycles

  摘要：

  Synthesis of cyclopentenone derivatives fused to oxygen heterocycles by means of the intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined for a variety of cases in which the tethering chain features a stereogenic center. In some cases, this process proceeds with a very high degree of stereoselectivity; however, the extent and direction of relative asymmetric induction is very dependent upon the position of the chiral atom within the tethering chain and the length of the tethering chain. In the best case, featuring a two-carbon tether and a stereogenic center at the homopropargylic position (complex 1N), the heterocyclic ring was produced with 97:3 selectivity for the cis heterocycle (3N). In the worst case, featuring a three-carbon tether and a stereogenic center at the homopropargylic position (complexes 1F and ii), no stereoselectivity was observed. Improvement in stereoselectivity was noticed when terminal alkynes were replaced by silylated alkynes and when proton sources were eliminated from the reaction.

  DOI：

  10.1021/jo982144q
• 作为产物：
  描述：

  (2S)-4-[(tert-butyldimethylsilyl)oxy]butan-2-ol 在 正丁基锂 、 四丙基高钌酸铵 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 1-(tert-butyldimethylsiloxy)-3-methyl-3-butene
  参考文献：
  名称：

  使用化学合成的（S）-和（R）-[2-2H]异戊烯基二磷酸酯对金黄色葡萄球菌的II型异戊烯基二磷酸异构酶进行立体化学分析。

  摘要：

  [化学反应：见正文]。为了研究来自金黄色葡萄球菌的II型异戊烯二磷酸（IPP）异构酶的催化作用，它是一种黄酮蛋白，可催化IPP与二磷酸二甲基烯丙基烯丙酯的相互转化，我们已经化学合成了（S）-和（R）-[2-2H] IPP对反应进行了立体化学分析。我们的结果表明，该酶的IPP的C-2去质子化是pro-R立体定向的，表明与I型酶相似的立体化学过程。

  DOI：

  10.1021/ol0524050

文献信息

• Alkene Ozonolysis in the Presence of Diazo Functionality: Accessing an Intermediate for Squalestatin Synthesis
  作者：Hasanain A. A. Almohseni、Younes Fegheh-Hassanpour、Tanzeel Arif、David M. Hodgson

  DOI：10.1055/s-0039-1690180

  日期：2019.11

  cycloaddition between diazo and alkene functionality, and the tolerance of α-substituted α-diazoesters towards ozone in the presence of an alkene, led to chemoselective alkene ozonolysis of an ε-unsaturated-α-diazoester to give a key racemic diazoketone for the synthesis of 6,7-dideoxysqualestatin H5. Studies on both the propensity for intramolecular cycloaddition between diazo and alkene functionality, and the

  抽象的 对重氮和烯烃官能团之间分子内环加成的倾向以及在烯烃存在下α-取代的α-重氮酸酯对臭氧的耐受性的研究都导致ε-不饱和α-重氮酸酯的化学选择性烯烃臭氧分解，从而得到关键的外消旋重氮酮，用于合成6,7-二脱氧角鲨烯抑制素H5。 对重氮和烯烃官能团之间分子内环加成的倾向以及在烯烃存在下α-取代的α-重氮酸酯对臭氧的耐受性的研究都导致ε-不饱和α-重氮酸酯的化学选择性烯烃臭氧分解，从而得到关键的外消旋重氮酮，用于合成6,7-二脱氧角鲨烯抑制素H5。
• Enantioselective Hydrolysis of Functionalized 2,2-Disubstituted Oxiranes with Bacterial Epoxide Hydrolases
  作者：Andreas Steinreiber、Ingrid Osprian、Sandra F. Mayer、Romano V. A. Orru、Kurt Faber

  DOI：10.1002/1099-0690(200011)2000:22<3703::aid-ejoc3703>3.0.co;2-3

  日期：2000.11

  ether-oxygen to the stereogenic quaternary carbon center of the oxirane ring had a profound influence on the enantioselectivity, and several oxiranes were resolved with good to excellent selectivities. The enantiomerically enriched epoxides and vicinal diols thus obtained contain a useful “synthetic handle” in their side chain, which allows their use as building blocks in asymmetric synthesis.

  使用 11 种细菌菌株的环氧化物水解酶活性研究了带有各种氧官能团的 2,2-二取代环氧乙烷的生物水解。结果表明，活性和选择性强烈依赖于底物结构和生物催化剂。尽管具有游离羟基的底物没有被转化，但它们的类似物，被保护为醚，被广泛接受。这使得通过根据尺寸和极性正确选择醚组，可以方便地调制对映射性。发现醚-氧与环氧乙烷环的立体四元碳中心的距离对对映选择性有深远的影响，并且几种环氧乙烷以良好到极好的选择性分离。
• Preparation of Alkylmagnesium Reagents from Alkenes through Hydroboration and Boron-Magnesium Exchange
  作者：Markus A. Reichle、Bernhard Breit

  DOI：10.1002/anie.201201704

  日期：2012.6.4

  Tolerant: Alkylmagnesium reagents can be synthesized from alkenes through a sequence of hydroboration and subsequent boron–magnesium exchange using a method that tolerates different functional groups (see scheme). The resulting alkylmagnesium reagents can be used in carbon–carbon bond forming reactions, such as alkylation reactions or transition‐metal‐catalyzed cross‐coupling reactions.

  宽容：烷基镁试剂可从烯烃通过硼氢化反应和随后的硼镁交换的序列使用容忍不同的官能团的方法（参见方案）来合成。所得的烷基镁试剂可用于碳-碳键形成反应，例如烷基化反应或过渡金属催化的交叉偶联反应。
• Direct and Stereospecific Synthesis of <i>N</i> ‐H and <i>N</i> ‐Alkyl Aziridines from Unactivated Olefins Using Hydroxylamine‐ <i>O</i> ‐Sulfonic Acids
  作者：Zhiwei Ma、Zhe Zhou、László Kürti

  DOI：10.1002/anie.201705530

  日期：2017.8.7

  A RhII-catalyzed direct and stereospecific N-H- and N-alkyl aziridination of olefins is reported that uses hydroxylamine-O-sulfonic acids as inexpensive, readily available, and nitro group-free aminating reagents. Unactivated olefins, featuring a wide range of functional groups, are converted into the corresponding N-H or N-alkyl aziridines in good to excellent yields. This operationally simple, scalable

  据报道，Rh II催化的烯烃的直接和立体有择的N -H-和N-烷基叠氮化使用廉价的，容易获得的和无硝基的胺化试剂使用羟胺-O-磺酸。未活化的烯烃，具有宽范围的官能团的，被转化成相应的Ñ -H或ñ -烷基氮丙啶以良好至优异的产量。此操作简单，可扩展的转换在环境温度下有效进行，并且耐氧气和微量水分。
• 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。