2-(2-(allyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(2-(allyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-(2-(Allyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-(2-prop-2-enoxyphenyl)-1,3,2-dioxaborolane
• 化学式: C₁₅H₂₁BO₃
• 分子量: 260.141
• InChiKey: ZZDXCUHKANAGNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,3-二甲基-2-碘苯 、 2-(2-(allyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 1,2-bis(bis(3,5-dimethylphenyl)phosphanyl)benzene 、 copper(I) bromide 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以73%的产率得到3-(2,6-dimethylbenzyl)-2,3-dihydrobenzofuran
  参考文献：
  名称：

  Diarylation of Alkenes by a Cu-Catalyzed Migratory Insertion/Cross-Coupling Cascade

  摘要：

  A strategy for the catalytic diarylation of alkenes is presented. The method involves the migratory insertion of alkenes into an Ar-Cu complex to generate a new C(sp(3))-Cu complex, which subsequently undergoes reaction with an aryl iodide to constitute a vicinal diarylation of an alkene. The method provides access to benzofuran- and indoline-containing products. Furthermore, highly diastereoselective examples are presented, allowing access to complex, stereochemically rich structures from simple alkene starting materials.

  DOI：

  10.1021/ja509056j
• 作为产物：
  描述：

  1-allyloxy-2-iodobenzene 、 联硼酸频那醇酯 在 diethylzinc 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 24.5h， 以71%的产率得到2-(2-(allyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Design, Generation, and Synthetic Application of Borylzincate: Borylation of Aryl Halides and Borylzincation of Benzynes/Terminal Alkyne

  摘要：

  Borylzincate was generated in situ from dialkylzinc, diboron, and metal alkoxide. Model DFT calculations showed that although the formation of borylzincate is kinetically favorable, it is thermodynamically unfavorable. Therefore, we designed a successive reaction sequence that would provide a compensating energy gain. This enabled Zn-catalyzed borylation of aryl halides and borylzincation of benzynes and terminal alkyne from diborons without the need for any cocatalyst.

  DOI：

  10.1021/ja409748m

文献信息

• Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold
  作者：Luca Demonti、Nathalie Saffon‐Merceron、Nicolas Mézailles、Noel Nebra

  DOI：10.1002/chem.202102836

  日期：2021.11.5

  trifluoromethylation via AgI/AgIII redox shuttles are herein deciphered. This innovative cross-coupling, analogous to the CEL coupling popularized by copper, involves: i) easy AgI/AgIII 2e− oxidation; ii) phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) benzotrifluoride production from aryl-AgIII intermediates. Now, AgIIICF3 chemistry is safe and reachable from AgF, KF, CF3TMS and air.

  教银做伎俩。通过Ag I / Ag III氧化还原穿梭进行氧化三氟甲基化的最关键步骤在本文中被破译。这种创新的交叉耦合类似于铜普及的 CEL 耦合，包括：i)容易的 Ag I /Ag III 2 e -氧化；ii)苯连接到 Ag III 上；iii)硼到 Ag III芳基转移；和ⅳ）三氟甲苯产量从芳基的Ag III中间体。现在，Ag III CF 3化学是安全的，可以从 AgF、KF、CF 3 TMS 和空气中获得。
• Visible-Light-Induced Ni-Catalyzed Radical Borylation of Chloroarenes
  作者：Ya-Ming Tian、Xiao-Ning Guo、Ivo Krummenacher、Zhu Wu、Jörn Nitsch、Holger Braunschweig、Udo Radius、Todd B. Marder

  DOI：10.1021/jacs.0c08834

  日期：2020.10.21

  borylation reactions proceed via a radical process. EPR studies demonstrate that [Ni(IMes)2] undergoes very fast chlorine atom abstraction from aryl chlorides to give [NiI(IMes)2Cl] and aryl radicals. Control experiments indicate that light promotes the reaction of [NiI(IMes)2Cl] with aryl chlorides generating additional aryl radicals and [NiII(IMes)2Cl2]. The aryl radicals react with an anionic sp2-sp3

  报道了一种高选择性和通用的光诱导 C-Cl 硼酸化方案，该方案采用 [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) 进行氯芳烃的自由基硼酸化。这种光诱导系统在可见光 (400 nm) 下运行，并在室温下以优异的收率和高选择性实现了广泛的氯芳烃与 B2pin2 的硼化，从而证明了其广泛的实用性和官能团耐受性。机理研究表明，硼酸化反应是通过自由基过程进行的。EPR 研究表明，[Ni(IMes)2] 从芳基氯化物中快速提取氯原子，生成 [NiI(IMes)2Cl] 和芳基自由基。对照实验表明，光促进 [NiI(IMes)2Cl] 与芳基氯的反应，产生额外的芳基和 [NiII(IMes)2Cl2]。芳基与由 B2pin2 和 KOMe 形成的阴离子 sp2-sp3 乙硼烷 [B2pin2(OMe)]- 反应生成相应的硼化产物和 [Bpin(OMe)]•-
• Catalytic Enantioselective Diarylation of Alkenes
  作者：Wei You、M. Kevin Brown

  DOI：10.1021/jacs.5b10176

  日期：2015.11.25

  for the catalytic enantioselective diarylation of alkenes is presented. The method allowed for the synthesis of highly enantioenriched 2,3-dihydrobenzofurans and indolines containing molecules from readily available substrates. Furthermore, this method allowed for the enantioselective synthesis of quaternary carbons. Based on mechanism studies, the process likely functions by enantioselective insertion

  提出了一种烯烃催化对映选择性二芳基化的方法。该方法允许从容易获得的底物合成含有高度对映体的 2,3-二氢苯并呋喃和二氢吲哚分子。此外，该方法允许对映选择性合成季碳。根据机理研究，该过程可能通过将烯烃对映选择性插入 Ar-CuBenzP* 复合物以生成 Csp(3)-Cu 复合物来发挥作用。用 ArX 捕获该中间体导致形成所需产物。
• Design, Generation, and Synthetic Application of Borylzincate: Borylation of Aryl Halides and Borylzincation of Benzynes/Terminal Alkyne
  作者：Yuki Nagashima、Ryo Takita、Kengo Yoshida、Keiichi Hirano、Masanobu Uchiyama

  DOI：10.1021/ja409748m

  日期：2013.12.18

  Borylzincate was generated in situ from dialkylzinc, diboron, and metal alkoxide. Model DFT calculations showed that although the formation of borylzincate is kinetically favorable, it is thermodynamically unfavorable. Therefore, we designed a successive reaction sequence that would provide a compensating energy gain. This enabled Zn-catalyzed borylation of aryl halides and borylzincation of benzynes and terminal alkyne from diborons without the need for any cocatalyst.
• Diarylation of Alkenes by a Cu-Catalyzed Migratory Insertion/Cross-Coupling Cascade
  作者：Wei You、M. Kevin Brown

  DOI：10.1021/ja509056j

  日期：2014.10.22

  A strategy for the catalytic diarylation of alkenes is presented. The method involves the migratory insertion of alkenes into an Ar-Cu complex to generate a new C(sp(3))-Cu complex, which subsequently undergoes reaction with an aryl iodide to constitute a vicinal diarylation of an alkene. The method provides access to benzofuran- and indoline-containing products. Furthermore, highly diastereoselective examples are presented, allowing access to complex, stereochemically rich structures from simple alkene starting materials.