4,4,5,5-tetramethyl-2-(1-phenylbutyl)-1,3,2-dioxaborolane | 1438827-34-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,4,5,5-tetramethyl-2-(1-phenylbutyl)-1,3,2-dioxaborolane
• 英文别名: 4,4,5,5-Tetramethyl-2-(1-phenylbutyl)-1,3,2-dioxaborolane
• CAS: 1438827-34-9
• 化学式: C₁₆H₂₅BO₂
• 分子量: 260.184
• InChiKey: QCQYNPBZMZCGRH-UHFFFAOYSA-N

物化性质

• 沸点：
  312.9±21.0 °C(predicted)
• 密度：
  0.95±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  4,4,5,5-tetramethyl-2-(1-phenylbutyl)-1,3,2-dioxaborolane 在 sodium perborate tetrahydrate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 4.0h， 以86%的产率得到1-苯基-1-丁醇
  参考文献：
  名称：

  NiH催化的含硼烯烃的远程加氢芳基化反应可快速获得高度官能化的硼酸烷基酯。

  摘要：

  相对简单且容易获得的前体的直接和选择性官能化以产生高度官能化的硼酸烷基酯是合成上有用的方法。本文中，我们报道了NiH催化的远程氢芳构化过程，该过程可以通过链走和随后的交叉偶联的协同组合，在温和的条件下在烷基硼酸酯的相邻碳原子上引入芳基。通过具有中等对映选择性的初步实验，表明还可以实现不对称形式。

  DOI：

  10.1002/anie.201907185
• 作为产物：
  描述：

  dimethyl-[2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butyl]phenyl]silane 在 三甲基氯硅烷 、 水 、 potassium iodide 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以97%的产率得到4,4,5,5-tetramethyl-2-(1-phenylbutyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  Iridium-Catalyzed Borylation of Secondary Benzylic C–H Bonds Directed by a Hydrosilane

  摘要：

  Most functionalizations of C-H bonds by main-group reagents occur at aryl or methyl groups. We describe a highly regioselective borylation of secondary benzylic C-H bonds catalyzed by an iridium precursor and 3,4,7,8-tetramethyl-1,10-phenanthroline as the ligand. The reaction is directed to the benzylic position by a hydrosilyl substituent. This hydrosilyl directing group is readily deprotected or transformed to other functional groups after the borylation reaction, providing access to a diverse set of secondary benzylboronate esters by C-H borylation chemistry.

  DOI：

  10.1021/ja403462b

文献信息

• Palladium-catalyzed regioselective hydroboration of aryl alkenes with B₂pin₂
  作者：Jiuzhong Huang、Wuxin Yan、Chaowei Tan、Wanqing Wu、Huanfeng Jiang

  DOI：10.1039/c7cc09432a

  日期：——

  A palladium(II)-catalyzed hydroboration of aryl alkenes with stable and easy-to-handle (pinacolato)diboron (B2pin2) under mild conditions has been developed. Acetic acid acted as the solvent and the hydrogen source, which has been identified by deuterium experiments. Notably, isomerization–hydroboration of allyl benzene derivatives was observed. As a result, a series of benzyl boronic esters were obtained

  在温和的条件下，已开发出钯（II）催化的具有稳定且易于处理的（频哪醇）二硼烷（B 2 pin 2）的芳基烯烃加氢硼化反应。乙酸充当了溶剂和氢源，这已通过氘实验确定。值得注意的是，观察到烯丙基苯衍生物的异构化-硼氢化。结果，以中等至优异的产率获得了一系列苄基硼酸酯，并且具有唯一的区域选择性。
• Cobalt-Catalyzed Hydroboration of Alkenes, Aldehydes, and Ketones
  作者：Sem Raj Tamang、Deepika Bedi、Sara Shafiei-Haghighi、Cecilia R. Smith、Christian Crawford、Michael Findlater

  DOI：10.1021/acs.orglett.8b02775

  日期：2018.11.2

  An operationally convenient and general method for hydroboration of alkenes, aldehydes, and ketones employing Co(acac)3 as a precatalyst is reported. The hydroboration of alkenes in the presence of HBpin, PPh3, and NaOtBu affords good to excellent yields with high Markovnikov selectivity with up to 97:3 branched/linear selectivity. Moreover, Co(acac)3 could be used effectively to hydroborate aldehydes

  报道了使用Co（acac）3作为预催化剂对烯烃，醛和酮进行氢硼化的操作方便且通用的方法。在HBpin，PPh 3和NaO t Bu存在下，烯烃进行硼氢化可提供良好的产率，并具有高的马尔可夫尼科夫选择性和高达97：3的支链/线性选择性。而且，在温和的反应条件下，在不存在添加剂的情况下，Co（acac）3可有效地用于硼氢化醛和酮。醛基的分子间和分子内化学选择性还原发生在酮官能团之上。
• Selective Benzylic CH‐Borylations by Tandem Cobalt Catalysis
  作者：Pradip Ghosh、Roland Schoch、Matthias Bauer、Axel Jacobi von Wangelin

  DOI：10.1002/anie.202110821

  日期：2022.1.3

  An inexpensive cobalt catalyst enables the combination of benzylic CH-borylation and dehydrocoupling to an overall acceptorless dehydrogenative functionalization of hydrocarbons at mild conditions. Mechanistic studies indicate a tandem catalysis via molecular CoI catalysts.

  廉价的钴催化剂能够将苄基CH-硼基化和脱氢偶联相结合，在温和条件下实现烃类的整体无受体脱氢官能化。机理研究表明通过分子钴催化剂进行串联催化。
• Alkene Isomerization–Hydroboration Promoted by Phosphine-Ligated Cobalt Catalysts
  作者：Margaret L. Scheuermann、Elizabeth J. Johnson、Paul J. Chirik

  DOI：10.1021/acs.orglett.5b01135

  日期：2015.6.5

  Generated in situ from air-stable cobalt precursors or readily synthesized using NaHBEt3, (PPh3)(3)CoH(N-2) was found to be an effective catalyst for the hydroboration of alkenes. Unlike previous base-metal catalysts for alkene isomerizationhydroboration which favor the incorporation of boron at terminal positions, (PPh3)(3)CoH(N-2) promotes boron incorporation adjacent to pi-systems even in substrates where the alkene is at a remote position, enabling a unique route to 1,1-diboron compounds from alpha,omega-dienes.
• Iridium-Catalyzed Borylation of Secondary Benzylic C–H Bonds Directed by a Hydrosilane
  作者：Seung Hwan Cho、John F. Hartwig

  DOI：10.1021/ja403462b

  日期：2013.6.5

  Most functionalizations of C-H bonds by main-group reagents occur at aryl or methyl groups. We describe a highly regioselective borylation of secondary benzylic C-H bonds catalyzed by an iridium precursor and 3,4,7,8-tetramethyl-1,10-phenanthroline as the ligand. The reaction is directed to the benzylic position by a hydrosilyl substituent. This hydrosilyl directing group is readily deprotected or transformed to other functional groups after the borylation reaction, providing access to a diverse set of secondary benzylboronate esters by C-H borylation chemistry.