(E)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane | 165904-17-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: (E)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane
• 英文别名: Trimethyl[(2E)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-en-1-yl]silane；trimethyl-[(E)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enyl]silane
• CAS: 165904-17-6
• 化学式: C₁₂H₂₅BO₂Si
• 分子量: 240.226
• InChiKey: LNQUAQSDSWVSDE-CMDGGOBGSA-N

物化性质

• 沸点：
  234.6±42.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane 在 iron(III) chloride 、 platinum(II) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 2-(5-butyl-3-(p-tolyl)bicyclo[3.1.0]hexan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Tandem Reactions Involving 1-Silyl-3-Boryl-2-Alkenes. New Access to (Z)-1-Fluoro-1-Alkenes, Allyl Fluorides, and Diversely α-Substituted Allylboronates

  摘要：

  The reactions of 1-silyl-3-boryl-2-alkenes with various electrophilic reagents (Selecffluor, N-halosuccinimides, benzhydryl, and propargylic alcohols In the presence of a Lewis acid, N-alkoxycarbonyliminium ion) have been investigated as new routes to alpha-substituted allylboronates. Further functional transformations, including allylboration, Suzuki coupling, protodeboronation, and cycloisomerization, have been carried out to illustrate the synthetic potential of these gamma-borylallylsilanes.

  DOI：

  10.1021/ol4000263
• 作为产物：
  描述：

  频哪醇 在 Schwartz's reagent 作用下， 以 二氯甲烷 为溶剂， 反应 85.0h， 生成 (E)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane
  参考文献：
  名称：

  Tandem Reactions Involving 1-Silyl-3-Boryl-2-Alkenes. New Access to (Z)-1-Fluoro-1-Alkenes, Allyl Fluorides, and Diversely α-Substituted Allylboronates

  摘要：

  The reactions of 1-silyl-3-boryl-2-alkenes with various electrophilic reagents (Selecffluor, N-halosuccinimides, benzhydryl, and propargylic alcohols In the presence of a Lewis acid, N-alkoxycarbonyliminium ion) have been investigated as new routes to alpha-substituted allylboronates. Further functional transformations, including allylboration, Suzuki coupling, protodeboronation, and cycloisomerization, have been carried out to illustrate the synthetic potential of these gamma-borylallylsilanes.

  DOI：

  10.1021/ol4000263

文献信息

• PSiP-Pincer Type Palladium-Catalyzed Dehydrogenative Borylation of Alkenes and 1,3-Dienes
  作者：Naohiro Kirai、Shoichiro Iguchi、Tatsuyoshi Ito、Jun Takaya、Nobuharu Iwasawa

  DOI：10.1246/bcsj.20130004

  日期：2013.7.15

  Dehydrogenative borylation of alkenes and 1,3-dienes was realized by carrying out the reaction in the presence of bis(pinacolato)diboron (B2pin2) and a catalytic amount of PSiP-pincer palladium complex. This protocol has the following notable features. 1) Monoanionic nature of the PSiP-pincer ligand prevents the formation of boryl(hydrido)- or dihydridopalladium species, enabling synthesis of various vinyl- or dienylboronic esters in good yield from a 1:1 mixture of B2pin2 and alkenes or 1,3-dienes without forming hydroboration or hydrogenation products. 2) Due to the strong trans influence of the silicon atom, PSiP-pincer palladium complex showed high activity toward migratory insertion. 3) Suppression of these side-reactions and the high reactivity of the PSiP-pincer palladium complex enabled an efficient, successive dehydrogenative borylation to give 1,1- or 1,2-diborylated products depending on the kind of substituent on alkenes by using more than 2 equivalents of B2pin2. Mechanistic study revealed that PSiP-pincer borylpalladium complex was generated from hydridopalladium complex and B2pin2, and this complex underwent alkene insertion followed by β-hydride elimination to give alkenylboronic ester with regeneration of the hydridopalladium complex.

  通过在双(频哪醇)二硼(B2pin2)和催化量的PSiP-螯合钯配合物存在下进行反应，实现了烯烃和1,3-二烯的脱氢硼化反应。该方案具有以下显著特点：1) PSiP-螯合配体的单阴离子性质阻止了硼(氢)化物或二氢化钯物种的形成，从而能够从B2pin2和烯烃或1,3-二烯的1:1混合物中以良好的产率合成各种乙烯基或二烯基硼酸酯，而不形成氢硼化或氢化产物。2) 由于硅原子的强横向影响，PSiP-螯合钯配合物显示出高的迁移插入活性。3) 抑制这些副反应和PSiP-螯合钯配合物的高反应性使得高效连续脱氢硼化反应成为可能，从而根据烯烃上取代基的种类，使用超过2当量的B2pin2，生成1,1-或1,2-二硼化产物。机理研究表明，PSiP-螯合硼化钯配合物由氢化钯配合物和B2pin2生成，该配合物经过烯烃插入和β-氢消除，生成烯基硼酸酯，并再生氢化钯配合物。
• Synthesis of tri-substituted vinyl boronates via ruthenium-catalyzed olefin cross-metathesis
  作者：Christie Morrill、Timothy W. Funk、Robert H. Grubbs

  DOI：10.1016/j.tetlet.2004.08.069

  日期：2004.10

  Tri-substituted vinyl pinacol boronates, which are key reactive intermediates in a variety of transformations, are synthesized using ruthenium-catalyzed olefin cross-metathesis of α-substituted vinyl boronates and various alkenes. Cross-metathesis of 2-isopropenyl pinacol boronate proceeds with moderate yield and high Z-selectivity when sterically unhindered cross partners are used. Cross-metathesis

  三取代的乙烯基频哪醇硼酸酯是各种转化中的关键反应中间体，是使用钌催化的α-取代的硼酸乙烯基酯与各种烯烃的交叉复分解反应合成的。当使用空间不受阻碍的交叉伙伴时，2-异丙烯基频哪醇硼酸酯的交叉复分解以中等收率和高Z-选择性进行。还实现了具有比甲基更大的α-取代基的硼酸乙烯基酯的交叉复分解。在这些情况下，产率和Z-选择性较低，并且交叉复分解反应的成功高度依赖于围绕α-取代的乙烯基硼酸酯的双键的空间体积。
• Tropylium-Promoted Hydroboration Reactions: Mechanistic Insights <i>Via</i> Experimental and Computational Studies
  作者：Nhan N. H. Ton、Binh Khanh Mai、Thanh Vinh Nguyen

  DOI：10.1021/acs.joc.1c01208

  日期：2021.7.2

  hydroboration reaction of alkynes. A broad range of vinylboranes can be easily accessed via this metal-free protocol. Similar hydroboration reactions of alkenes and epoxides can also be efficiently catalyzed by the same tropylium catalysts. Experimental studies and DFT calculations suggested that the reaction follows an uncommon mechanistic pathway, which is triggered by the hydride abstraction of pinacolborane

  炔烃的硼氢化反应是合成有机硼化合物最强大的工具之一，有机硼化合物是交叉偶联化学的通用前体。这种类型的反应传统上是由过渡金属或主族催化剂介导的。在此，我们报告了一种使用通常称为有机氧化剂和路易斯酸的镨盐来促进炔烃的硼氢化反应的新方法。通过这种无金属协议，可以轻松访问范围广泛的乙烯基硼烷。烯烃和环氧化物的类似硼氢化反应也可以由相同的托鎓催化剂有效催化。实验研究和 DFT 计算表明，该反应遵循一种不常见的机制途径，这是由频哪醇硼烷与 tropylium 离子的氢化物提取所触发的。接下来是一系列原位反离子活化的取代基交换以生成促进硼氢化反应的硼中间体。
• Tris(2,4,6-trifluorophenyl)borane: An Efficient Hydroboration Catalyst
  作者：James R. Lawson、Lewis C. Wilkins、Rebecca L. Melen

  DOI：10.1002/chem.201703109

  日期：2017.8.16

  The metal‐free catalyst tris(2,4,6‐trifluorophenyl)borane has demonstrated its extensive applications in the 1,2‐hydroboration of numerous unsaturated reagents, namely alkynes, aldehydes and imines, consisting of a wide array of electron‐withdrawing and donating functionalities. A range of over 50 borylated products are reported, with many reactions proceeding with low catalyst loading under ambient

  无金属催化剂三（2,4,6-三氟苯基）硼烷已证明其在多种不饱和试剂的1,2-氢硼化中具有广泛的应用，这些不饱和试剂包括炔烃，醛和亚胺，其中包括大量的吸电子和捐赠功能。据报道，有超过50种硼化产物，在环境条件下，许多反应都是在低催化剂负载下进行的。在醛和亚胺的情况下，这些频哪醇硼酸酯可以容易地水解以留下相应的醇和胺，而炔基底物产生乙烯基硼烷。这对有机化学家来说具有很大的合成用途。
• Efficient Synthesis of Diborylalkenes from Alkenes and Diboron by a New PSiP-Pincer Palladium-Catalyzed Dehydrogenative Borylation
  作者：Jun Takaya、Naohiro Kirai、Nobuharu Iwasawa

  DOI：10.1021/ja205186k

  日期：2011.8.24

  as 1,1-, trans-1,2-, and cyclic 1,2-diborylalkenes from alkenes and diboron was achieved for the first time. Selective preparation of di- and monoborylalkenes was also realized by the appropriate choice of reaction conditions. The reaction was found to proceed via a new mechanism of dehydrogenative borylation through a monoborylpalladium complex bearing an anionic PSiP-pincer ligand as a key intermediate

  首次实现了以烯烃和二硼为原料高效合成1,1-、反式-1,2-和环状1,2-二硼基烯烃等多种二硼基烯烃。Selective preparation of di- and monoborylalkenes was also realized by the appropriate choice of reaction conditions. 发现该反应通过一种新的脱氢硼化机制进行，以带有阴离子PSiP-钳状配体的单硼基钯配合物为关键中间体，实现了有效的硼化而不牺牲烯烃的硼氢化或氢化。