(Z)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane | 165904-30-3

• 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: (Z)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane
• 英文别名: trimethyl[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl]silane；trimethyl-[(Z)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enyl]silane
• CAS: 165904-30-3
• 化学式: C₁₂H₂₅BO₂Si
• 分子量: 240.226
• InChiKey: LNQUAQSDSWVSDE-HJWRWDBZSA-N

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：

  (Z)-trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane 、 Boc-D-苯丙氨酸 在 碳酸氢钠 、 Selectfluor 、 水 作用下， 以 乙腈 为溶剂， 反应 20.0h， 生成 t-butyl (2R,E)-6-fluoro-3-hydroxy-1-phenylhex-5-en-2-ylcarbamate 、 t-butyl (2R,Z)-6-fluoro-3-hydroxy-1-phenylhex-5-en-2-ylcarbamate
  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：

  4,4,5,5-tetramethyl-2-(3-trimethylsilyl-1-propynyl)-1,3,2-dioxaborolane 在 喹啉 、 氢气 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 以77%的产率得到(Z)-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。
• 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。
• Tandem Reactions Involving 1-Silyl-3-Boryl-2-Alkenes. New Access to (<i>Z</i>)-1-Fluoro-1-Alkenes, Allyl Fluorides, and Diversely α-Substituted Allylboronates
  作者：Aurélie Macé、Fabien Tripoteau、Qian Zhao、Eric Gayon、Emmanuel Vrancken、Jean-Marc Campagne、Bertrand Carboni

  DOI：10.1021/ol4000263

  日期：2013.2.15

  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.