4,4,5,5-tetramethyl-2-(2-methylphenethyl)-1,3,2-dioxaborolane | 1431792-80-1

• 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-(2-methylphenethyl)-1,3,2-dioxaborolane
• 英文别名: 1,3,2-Dioxaborolane, 4,4,5,5-tetramethyl-2-[2-(2-methylphenyl)ethyl]-；4,4,5,5-tetramethyl-2-[2-(2-methylphenyl)ethyl]-1,3,2-dioxaborolane
• CAS: 1431792-80-1
• 化学式: C₁₅H₂₃BO₂
• 分子量: 246.157
• InChiKey: PIFVWBYKAJUBLW-UHFFFAOYSA-N

物化性质

• 沸点：
  311.3±21.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.63
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 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-(2-methylphenethyl)-1,3,2-dioxaborolane 在 potassium hydrogen bifluoride 作用下， 以 水 、 乙腈 为溶剂， 反应 1.0h， 以52%的产率得到potassium trifluoro(2-methylphenethyl)borate
  参考文献：
  名称：

  Conformational restriction approach to BACE1 inhibitors II: SAR study of the isocytosine derivatives fixed with a cis-cyclopropane ring

  摘要：

  To improve the efficacy of the conformationally restricted BACE1 inhibitors, structural modifications were investigated using two strategies: (a) modification of the terminal aromatic ring and (b) insertion of a spacer between the aromatic rings. In the latter approach, another type of inhibitor 17 bearing an ethylene spacer between two aromatic rings was found to exhibit good BACE1 inhibitory activity, while the corresponding conformationally unrestricted compound 25 showed no activity. This result revealed an interesting effect of a conformational restriction with a cyclopropane ring. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2013.03.056
• 作为产物：
  描述：

  2-(2-methylphenethoxy)benzo[d]thiazole 在 4-二甲氨基吡啶 、 氮 、 三乙胺 作用下， 反应 21.0h， 生成 4,4,5,5-tetramethyl-2-(2-methylphenethyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  烷基杂芳基醚惰性 C(sp3)–O 键的光诱导硼化

  摘要：

  开发了在 4-二甲基氨基吡啶 (DMAP) 和双(儿茶酚)二硼烷 (B 2 cat 2 )存在下，具有非常负还原电位的烷基杂芳基醚的光诱导还原 C 烷基 -O 硼基化。尽管还原能力很高，但各种具有可靠官能团的底物以及源自天然产物和医药相关化合物的醚都具有良好的耐受性。机理研究表明，由醚与 B 2 cat 2和 DMAP 加合物形成的电子供体-受体复合物中应该涉及单内电子转移过程。

  DOI：

  10.1021/acs.orglett.3c02038

文献信息

• Silver-Catalyzed Hydroboration of C–X (X = C, O, N) Multiple Bonds
  作者：Vipin K. Pandey、Chandra Shekhar Tiwari、Arnab Rit

  DOI：10.1021/acs.orglett.1c00106

  日期：2021.3.5

  AgSbF6 was developed as an effective catalyst for the hydroboration of various unsaturated functionalities (nitriles, alkenes, and aldehydes). This atom-economic chemoselective protocol works effectively under low catalyst loading, base- and solvent-free moderate conditions. Importantly, this process shows excellent functional group tolerance and compatibility with structurally and electronically diverse

  AgSbF 6被开发为各种不饱和官能团（腈，烯烃和醛）进行硼氢化的有效催化剂。这种原子经济的化学选择性方案可在低催化剂负载，无碱和无溶剂的中等条件下有效地发挥作用。重要的是，该方法显示出优异的官能团耐受性以及与结构和电子多样化底物的相容性（> 50个实例）。机理研究表明，该反应通过自由基途径进行。此外，显示出所获得的N，N-二硼烷基胺是用于酰胺合成的有用的前体。
• 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 Synthesis of Alkylboronates by Copper(I)-Catalyzed Borylation of Allyl or Vinyl Arenes
  作者：Yanmei Wen、Jianying Xie、Chunmei Deng、Chaode Li

  DOI：10.1021/jo502606x

  日期：2015.4.17

  An efficient copper-catalyzed borylation reaction of allyl or vinyl arenes with bis(pinacolato)diboron has been developed, without using ligands. Markovnikov-selectivity is observed in the borylation of allyl arenes with bis(pinacolato)diboron, while the regioselectivity is completely opposite when styrene derivatives are used as substrates. A mechanism involving Cu–B species regioselectively adding

  已经开发了不使用配体的烯丙基或乙烯基芳烃与双（频哪醇）二硼的有效的铜催化的硼化反应。在烯丙基芳烃与双（频哪醇）二硼化的烯丙基化中观察到马尔可夫尼科夫选择性，而当使用苯乙烯衍生物作为底物时区域选择性完全相反。涉及的Cu-B物种区域选择性地加入烯烃双键以形成烷基铜或ηA机构3 -苄基铜中间体，随后是质子化，得到的产品，提出。
• Markovnikov-Selective Hydroboration of Vinylarenes Catalyzed by a Cobalt(II) Coordination Polymer
  作者：Guoqi Zhang、Jing Wu、Sihan Li、Sean Cass、Shengping Zheng

  DOI：10.1021/acs.orglett.8b03431

  日期：2018.12.21

  Highly efficient and practical hydroboration of alkenes has been catalyzed by an inexpensive and air-stable cobalt(II) coordination polymer (CP) in the presence of KOtBu. Complete conversion of alkenes to alkylboronates were performed within just 5 min with low catalyst loading (0.025 mol %), achieving the record high turnover frequencies of up to 47 520 h–1. For a range of vinylarenes, unusual Markovnikov

  在KO t Bu存在下，廉价且空气稳定的钴（II）配位聚合物（CP）催化了烯烃的高效，实用的硼氢化反应。在短短5分钟内以低催化剂负载量（0.025 mol％）将烯烃完全转化为烷基硼酸酯，实现了高达47 520 h –1的创纪录高周转率。对于一定范围的乙烯基芳烃，观察到了异常的马尔可夫尼科夫选择性。
• Cobalt-Catalyzed Regioselective Hydroboration of Terminal Alkenes
  作者：Guoqi Zhang、Jing Wu、Man Wang、Haisu Zeng、Jessica Cheng、Michelle C. Neary、Shengping Zheng

  DOI：10.1002/ejoc.201701047

  日期：2017.10.17

  Cobalt(II) catalysts based on flexible PNP or NNN ligands were explored for the regioselective hydroboration of alkenes. A known CoII–PNP pincer complex was found to efficiently catalyze alkene hydroboration with excellent anti-Markovnikov selectivity, whereas a newly synthesized dinuclear CoII–NNN complex was found to catalyze the hydroboration of a range of aromatic terminal alkenes with good Markovnikov

  探索了基于柔性 PNP 或 NNN 配体的钴 (II) 催化剂用于烯烃的区域选择性硼氢化。发现已知的 CoII-PNP 钳形配合物以优异的抗马尔科夫尼科夫选择性有效催化烯烃硼氢化反应，而发现新合成的双核 CoII-NNN 配合物以良好的马尔科夫尼科夫选择性（高达98:2，桶/升）。这代表了使用廉价、柔性配体负载的双核钴催化剂对烯烃进行硼氢化反应中马尔可夫尼科夫选择性的罕见例子。