(E)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-5-enenitrile | 141091-31-8

• 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: (E)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-5-enenitrile
• 英文别名: (5e)-6-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)hex-5-enenitrile
• CAS: 141091-31-8
• 化学式: C₁₂H₂₀BNO₂
• 分子量: 221.107
• InChiKey: KHMNZDWKJKKHNU-VQHVLOKHSA-N

物化性质

• 沸点：
  285.7±50.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  42.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-5-enenitrile 在 sodium periodate 、 ammonium acetate 、 水 作用下， 以 丙酮 为溶剂， 生成 5-cyanopent-1-enylboronic acid
  参考文献：
  名称：

  Preparation of α-Imino Aldehydes by [1,3]-Rearrangements of O-Alkenyl Oximes

  摘要：

  The synthesis of alpha-imino aldehydes has been achieved through the thermal [1,3]-rearrangement of O-alkenyl benzophenone oximes. A copper. mediated C-O bond coupling between benzophenone oxime and alkenyl boronic acids provides facile access to the required O-alkenyl oximes and a Horner-Wadsworth-Emmons olefination can be applied to the a-imino aldehyde products to give gamma-imino-alpha,beta-unsaturated esters. The scope of the method is described and mechanistic experiments are discussed.

  DOI：

  10.1021/ol402237w
• 作为产物：
  描述：

  己炔腈 、 联硼酸频那醇酯 在 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene silver chloride 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 7.0h， 以84%的产率得到(E)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-5-enenitrile
  参考文献：
  名称：

  Silver-Catalyzed Highly Regioselective Formal Hydroboration of Alkynes

  摘要：

  A silver(I)-N-heterocyclic carbene complex has proven to be a potent catalyst for formal hydroboration of alkynes, providing a variety of borylalkenes in regio- and stereoselective manners. Under the silver catalysis, allenes also undergo regioselective hydroboration to give borylalkenes.

  DOI：

  10.1021/ol501465x

文献信息

• [EN] INHIBITORS OF ECTONUCLEOTIDE PYROPHOSPHATASE/PHOSPHODIESTERASE 1 (ENPP1) AND METHODS OF USE THEREOF<br/>[FR] INHIBITEURS DE L'ECTONUCLÉOTIDE PYROPHOSPHATASE/PHOSPHODIESTÉRASE 1 (ENPP1) ET LEURS PROCÉDÉS D'UTILISATION
  申请人：STINGRAY THERAPEUTICS INC

  公开号：WO2021158829A1

  公开（公告）日：2021-08-12

  Compounds and methods for their preparation and use as therapeutic or prophylactic agents, for example for treatment of cancer, bacterial or viral diseases by targeting Ectonucleotide Pyrophosphatase/Phosphodiesterase-1 (ENPP1).

  化合物及其制备和使用方法，用作治疗或预防剂，例如通过靶向胞苷酸焦磷酸酶/磷酸二酯酶-1（ENPP1）来治疗癌症、细菌或病毒性疾病。
• Nickel‐Catalyzed Regioselective Hydroalkylation and Hydroarylation of Alkenyl Boronic Esters
  作者：Srikrishna Bera、Xile Hu

  DOI：10.1002/anie.201907045

  日期：2019.9.23

  catalyzed hydrocarbonation, linear selectivity is most often obtained because of the relative stability of the linear Ni-alkyl intermediate over its branched counterpart. Herein, we show that the boronic pinacol ester (Bpin) group directs a Ni-catalyzed hydrocarbonation to occur at its adjacent carbon center, resulting in formal branch selectivity. Both alkyl and aryl halides can be used as electrophiles

  金属氢化物催化烯烃的烃化反应是从容易获得的烯烃中构建新的碳-碳键的有效方法。然而，烃化的区域选择性仍然难以控制。在氢化镍（NiH）催化的烃化反应中，由于线性Ni-烷基中间体相对于其支链对应物的相对稳定性，最经常获得线性选择性。在这里，我们显示硼烷频哪醇酯（Bpin）基团指导Ni催化的烃化反应发生在其相邻的碳中心，从而形成正式的分支选择性。烷基卤化物和芳基卤化物均可在此烃化反应中用作亲电子试剂，从而提供了广泛的仲烷基Bpin衍生物的途径，它们是合成化学中的重要组成部分。
• Nickel-Catalyzed Highly Selective Hydroalkenylation of Alkenyl Boronic Esters to Access Allyl Boron
  作者：Penglin Zhang、Min Zhang、Yuqi Ji、Mimi Xing、Qian Zhao、Chun Zhang

  DOI：10.1021/acs.orglett.0c02923

  日期：2020.11.6

  Allyl boron derivatives are valuable building blocks in the synthesis of natural products and bioactive molecules. Herein, a practical strategy of nickel-catalyzed highly selective hydroalkenylation of alkenyl boronic esters was developed. Under the mild reaction conditions, a variety of allyl boronic esters were accessed with excellent chemo- and regioselectivity. The mechanism of this transformation

  烯丙基硼衍生物是天然产物和生物活性分子合成中的重要组成部分。本文中，开发了镍催化的烯基硼酸酯的高选择性加氢烯基化的实用策略。在温和的反应条件下，可以得到具有优异的化学和区域选择性的各种烯丙基硼酸酯。通过控制实验和动力学研究说明了这种转化的机理。
• Cobalt-Catalyzed Hydroboration of Terminal and Internal Alkynes
  作者：María J. González、Felix Bauer、Bernhard Breit

  DOI：10.1021/acs.orglett.1c02854

  日期：2021.11.5

  A novel methodology to access synthetically versatile vinylboronic esters through a ligand-controlled cobalt-catalyzed hydroboration of terminal and internal alkynes is reported. The approach relies on the in situ reduction of Co(II) by H-BPin in the presence of bisphosphine ligands generating catalytically active Co(I) hydride complexes. This procedure avoids the use of stoichiometric amounts of base

  报道了一种通过配体控制的钴催化的末端和内部炔烃的硼氢化反应获得合成通用乙烯基硼酸酯的新方法。该方法依赖于H-BPin 在双膦配体存在下原位还原 Co(II)，生成具有催化活性的 Co(I) 氢化物复合物。该程序避免使用化学计量量的碱，并且不会产生含硼副产物，这转化为高官能团耐受性和原子经济性。
• Lewis acid catalysis: catalytic hydroboration of alkynes initiated by Piers' borane
  作者：Mirco Fleige、Juri Möbus、Thorsten vom Stein、Frank Glorius、Douglas W. Stephan

  DOI：10.1039/c6cc05360b

  日期：——

  Terminal and internal alkynes are efficiently hydroborated to (E)-alkenyl pinacol boronic esters with excellent yields and selectivities using Piers' borane, (HB(C₆F₅)₂) as a pre-catalyst for the dissymmetrically gem-diborylated catalyst of the form RCH₂CR′(Bpin)(B(C₆F₅)₂).

  末端和内部炔烃可以高效地氢硼化为优异收率和选择性的(E)-烯基琼醇硼酯，使用皮尔斯硼烷(HB(C₆F₅)₂)作为非对称gem-双硼催化剂的前驱催化剂，其形式为RCH₂CR′(Bpin)(B(C₆F₅)₂)。