[2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl]trimethylsilane | 1325764-19-9

• 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: [2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl]trimethylsilane
• 英文别名: [(Z)-2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enyl]-trimethylsilane
• CAS: 1325764-19-9
• 化学式: C₁₈H₃₆B₂O₄Si
• 分子量: 366.189
• InChiKey: GRRJHLBKPBVEGI-WYMLVPIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.51
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl]trimethylsilane 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 potassium phosphate monohydrate 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 18.0h， 生成 methyl 2-(morpholino)-4-(4-methoxyphenyl)-5-(trimethylsilyl)pent-3-enoate
  参考文献：
  名称：

  Regio- and Stereocontrolled Access to γ-Boronated Unsaturated Amino Esters and Derivatives from (Z)-Alkenyl 1,2-Bis(boronates)

  摘要：

  The Borono-Mannich reaction of (Z)-1-alkene-1,2-diboronic esters proceeded regioselectively at the terminal C-B bond to afford (E)-gamma-boronated unsaturated amino esters in good yields. These compounds were then subjected to Suzuki couplings for the creation of diversely substituted olefinic amino acid systems. Several other functional transformations were also carried out to illustrate the synthetic utility of the Petasis products.

  DOI：

  10.1021/jo402237t
• 作为产物：
  描述：

  联硼酸频那醇酯 、 烯丙基三甲基硅烷 在 (CH₃Si(C₆H₃(CF₃)P(C₆H₃(CF₃)2)2)2)Pd(SO₃CF₃) 、 三乙基铝 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以82%的产率得到[2,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl]trimethylsilane
  参考文献：
  名称：

  通过新型 PSiP-Pincer 钯催化脱氢硼酸化反应从烯烃和二硼有效合成二硼基烯烃

  摘要：

  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。

  DOI：

  10.1021/ja205186k

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 1,1,1-Tris(boronates) from Vinylarenes by Co-Catalyzed Dehydrogenative Borylations–Hydroboration
  作者：Lei Zhang、Zheng Huang

  DOI：10.1021/jacs.5b11366

  日期：2015.12.23

  The selective preparation of 1,1,1-tris-(boronates) from vinylarenes and bis(pinacolato)diboron is described. The reactions occur at ambient temperature with excellent selectivity, high yields, and good functional group tolerance. Mechanistic studies suggest that Co(I)-catalyzed double dehydrogenative borylations generate a 1,1-diborylalkene intermediate, which undergoes hydroboration with pinacolborane formed in situ to yield 1,1,1-tris (boronate).