(E)-2-(4-methoxystyryl)-4,4,6-trimethyl-1,3,2-dioxaborinane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (E)-2-(4-methoxystyryl)-4,4,6-trimethyl-1,3,2-dioxaborinane
• 英文别名: 2-[(E)-2-(4-methoxyphenyl)ethenyl]-4,4,6-trimethyl-1,3,2-dioxaborinane
• 化学式: C₁₅H₂₁BO₃
• 分子量: 260.141
• InChiKey: CVURPMSGTSKXOA-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  19
• 可旋转键数：
  3
• 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：

  N-(o-iodobenzoyl)pyrrolidine 、 (E)-2-(4-methoxystyryl)-4,4,6-trimethyl-1,3,2-dioxaborinane 在 lithium tert-butoxide 作用下， 以 二甲基亚砜 为溶剂， 以77 %的产率得到(E)-(2-(4-methoxystyryl)pyrrolidin-1-yl)(phenyl)methanone
  参考文献：
  名称：

  10.1002/anie.202409310

  摘要：

  Allylic amines are prevalent and vital structural components present in many bioactive compounds and natural products. Additionally, they serve as valuable intermediates and building blocks, with wide‐ranging applications in organic synthesis. However, direct α‐C(sp3)‐H alkenylation of feedstock amines, particularly for the preparation of α‐alkenylated cyclic amines, has posed a longstanding challenge. Herein, we present a general, mild, operationally simple, and transition‐metal‐free α‐alkenylation of various readily available amines with alkenylborate esters in excellent E/Z ‐ and diastereoselectivities. This method features good compatibility with water and oxygen, broad substrate scope, and excellent functional group tolerance, thereby enabling the late‐stage modification of various complex molecules. Mechanistic studies suggest that the formation of a photoactive electron donor‐acceptor complex between 2‐iodobenzamide and the tetraalkoxyborate anion, which subsequently undergoes photoinduced single electron transfer and intramolecular 1,5‐hydrogen atom transfer to generate the crucial α‐amino radicals, is the key to success of this chemistry.

  DOI：

  10.1002/anie.202409310
• 作为产物：
  描述：

  2-甲基-2,4-戊二醇 在 palladium diacetate 硼酸三甲酯 、 三正丁胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 8.0h， 生成 (E)-2-(4-methoxystyryl)-4,4,6-trimethyl-1,3,2-dioxaborinane
  参考文献：
  名称：

  4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane: a superior 2-carbon building block for vinylboronate Heck couplings

  摘要：

  4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane is a superior reagent in terms of stability and reactivity in comparison to the vinylboronate pinacol ester, giving improved selectivity for Heck versus Suzuki coupling with both aryl iodides and bromides, and being easier to prepare and store. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.032

文献信息

• Transborylation of alkenylboranes with diboranes
  作者：Paula Dominguez-Molano、Gerard Bru、Oriol Salvado、Ricardo J. Maza、Jorge J. Carbó、Elena Fernández

  DOI：10.1039/d1cc05815k

  日期：——

  Exchange of boryl moieties between alkenylboranes and diboron reagents has been postulated as a stereospecific cross-metathesis pathway with concomitant formation of mixed diboron reagents. DFT calculations propose a mechanism for the stereocontrolled C(sp2)–B/B′–B′ cross-metathesis with both symmetric and non-symmetric diboron reagents.

  烯基硼烷和二硼试剂之间硼基部分的交换已被假定为一种立体特异性交叉复分解途径，伴随着混合二硼试剂的形成。DFT 计算提出了立体控制的 C(sp 2 )–B/B'–B' 交叉复分解与对称和非对称二硼试剂的机制。
• PEG-mediated recyclable borylative coupling of vinyl boronates with olefins
  作者：Jakub Szyling、Jędrzej Walkowiak、Tomasz Sokolnicki、Adrian Franczyk、Kinga Stefanowska、Mateusz Klarek

  DOI：10.1016/j.jcat.2019.07.009

  日期：2019.8

  repetitive batch borylative coupling of vinyl boronates with olefins by the effective immobilization of the [Ru(CO)Cl(H)(PCy3)2] catalyst in poly(ethylene glycols) with different molecular weights (Mw = 600–2000) and ending groups (OH, OMe, OSiMe3) or in biphasic poly(ethylene glycols)/supercritical CO2 (PEGs/scCO2) systems. Within this process, (E)-alkenyl boronates were obtained with high yields and

  本文报道了[Ru（CO）Cl（H）（PCy 3）2 ]催化剂在不同分子量的聚乙二醇中的有效固定，从而实现了硼酸乙烯基酯与烯烃的首次绿色环保可持续的批量硼烷基化偶联。（M w  = 600–2000）和端基（OH，OMe，OSiMe 3）或双相聚（乙二醇）/超临界CO 2（PEGs / scCO 2）系统中。在此过程中，（E以高收率和优异的立体选择性，区域选择性获得了α-烯基硼酸酯。通过使用2或4 mol％的Ru催化剂，最佳策略允许硼酸乙烯基酯与苯乙烯的交叉偶联分别重复多达8至16个重复批次。所描述的方法能够重用TM催化剂和溶剂，并减少或消除最终产品中挥发性有机溶剂和金属含量的使用，并获得较高的累积TON值（最高440）。双相系统还通过在CO 2流中有效提取产物，简化了分离程序。
• Mechanistic Studies on the Heck−Mizoroki Cross-Coupling Reaction of a Hindered Vinylboronate Ester as a Key Approach to Developing a Highly Stereoselective Synthesis of a C1−C7 <i>Z</i>,<i>Z</i>,<i>E</i>-Triene Synthon for Viridenomycin
  作者：Andrei S. Batsanov、Jonathan P. Knowles、Andrew Whiting

  DOI：10.1021/jo0626010

  日期：2007.3.1

  Mechanistic studies of the Heck−Mizoroki reaction of a vinylboronate ester with electronically different (four-substituted) aryl iodides shows that electron donors accelerate the cross-coupling, demonstrating that the oxidative addition step is not rate determining and that there is development of some degree of positive charge in the rate determining step. These results were used as a basis to allow

  乙烯基硼酸酯与电子上不同的（四取代）芳基碘化物的Heck-Mizoroki反应的机理研究表明，电子给体加速了交叉偶联，表明氧化加成步骤不是速率决定性的，并且有一定程度的发展。在速率确定步骤中的正电荷。这些结果被用作允许开发受阻乙烯基硼酸酯与电子缺陷型顺式-2-碘代丙烯酸甲酯的Heck-Mizoroki偶联反应条件的基础。通过一系列高度立体选择性的碘脱硼和Heck-Mizoroki反应，将生成的二烯基硼酸酯转变为三烯基碘化物前体，以进一步用于viridenomycin的总合成中。
• Design of Hemilabile N,N,N-Ligands in Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Benzyl/Propargyl Halides with Alkenylboronate Esters
  作者：Peng-Fei Wang、Jiao Yu、Kai-Xin Guo、Sheng-Peng Jiang、Ji-Jun Chen、Qiang-Shuai Gu、Ji-Ren Liu、Xin Hong、Zhong-Liang Li、Xin-Yuan Liu

  DOI：10.1021/jacs.2c00957

  日期：2022.4.13

  halides with alkenylboronate esters is an appealing tool in the assembly of synthetically valuable enantioenriched alkenes owing to the ready availability, low toxicity, and air/moisture stability of alkenylboronate esters. Here, we report a copper/chiral N,N,N-ligand catalytic system for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters (>80 examples) with good

  对映收敛基团 C(sp 3 )–C(sp 2) 烷基卤化物与烯基硼酸酯的交叉偶联是合成有价值的对映体富集烯烃的一种有吸引力的工具，因为烯基硼酸酯易于获得、低毒性和空气/水分稳定性。在这里，我们报告了一种铜/手性 N,N,N-配体催化体系，用于苄基/炔丙基卤化物与烯基硼酸酯（>80 个实例）的对映收敛交叉偶联，具有良好的官能团耐受性。成功的关键是通过在一个配位喹啉环的邻位安装空间位阻来合理设计半可溶性N,N,N-配体。因此，新设计的配体不仅可以促进三齿形式的自由基交叉偶联过程，还可以对二齿形式的高反应性烷基自由基进行对映控制。
• 4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane: a superior 2-carbon building block for vinylboronate Heck couplings
  作者：Andrew P. Lightfoot、Graham Maw、Carl Thirsk、Steven J.R. Twiddle、Andrew Whiting

  DOI：10.1016/j.tetlet.2003.08.032

  日期：2003.10

  4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane is a superior reagent in terms of stability and reactivity in comparison to the vinylboronate pinacol ester, giving improved selectivity for Heck versus Suzuki coupling with both aryl iodides and bromides, and being easier to prepare and store. (C) 2003 Elsevier Ltd. All rights reserved.