2-<(E)-1-octenyl>-1,3,2-benzodioxaborole | 147024-83-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2-<(E)-1-octenyl>-1,3,2-benzodioxaborole
• 英文别名: (E)-1-octenylboronic acid catechol ester；(E)-oct-1-en-1-yl-1,3,2-benzodioxaborole；2-{(E)-1-octenyl}-1,3,2-benzodioxaborole；2-oct-1-en-t-yl-benzo[1,3,2]dioxaborole；1,3,2-Benzodioxaborole, 2-(1-octenyl)-；2-[(E)-oct-1-enyl]-1,3,2-benzodioxaborole
• CAS: 147024-83-7；73349-13-0
• 化学式: C₁₄H₁₉BO₂
• 分子量: 230.115
• InChiKey: WTAGCSJISKIVFF-FMIVXFBMSA-N

物化性质

• 沸点：
  301.9±25.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  2-<(E)-1-octenyl>-1,3,2-benzodioxaborole 在 水 作用下， 反应 1.0h， 以82%的产率得到反-1-辛烯-1-基硼酸
  参考文献：
  名称：

  2-Pyrones possessing antimicrobial and cytotoxic activities

  摘要：

  The 2-pyrone sub-unit is found in a number of natural products possessing broad spectrum biological activity. Such compounds are validated as being capable of binding to specific protein domains and able to exert a remarkable range of biological effects. In an effort to identify synthetic 2-pyrones with interesting biological effects, herein we report the synthesis and biological evaluation of 4-substituted-6-methyl-2-pyrones. Synthetic routes to 4-alkyl/alkenyl/aryl/alkynyl-6-methyl-2-pyrones have been developed utilising Sonogashira, Suzuki and Negishi cross-coupling starting from readily available 4-bromo-6-methyl-2-pyrone. Specific conditions for each organometallic protocol were required for successful cross-coupling. In particular, a triethylamine/acetonitrile-base/solvent mixture was crucial to Sonogashira alkynylation of 4-bromo-6-methyl-2-pyrone, whereas thallium carbonate was a mandatory base for the Suzuki cross-coupling of trialkylboranes. The 2-pyrones demonstrate potent inhibitory activity against Bacillus subtilis, Escherichia coli, Staphylococcus aureus, Schizosaccharomyces pombe and Botrytis cinerea. The growth inhibitory activities of selected 2-pyrones were determined in A2780 human ovarian carcinoma and K562 human chronic myelogenous leukaemia cell lines using an in vitro cell culture system (MTT assay). These studies demonstrate that 4-phenylethynyl-, 4-tetrahydropyranylpropargyl ether- and 4-ethynyl-6-methyl-2-pyrones have excellent potential as a new class of anticancer agents. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.01.051
• 作为产物：
  描述：

  邻苯二酚 在 硼烷四氢呋喃络合物 、 bis(cyclohexanyl)borane 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 生成 2-<(E)-1-octenyl>-1,3,2-benzodioxaborole
  参考文献：
  名称：

  烯基从硼转移到硼制备(E)-1-烯基硼酸频哪醇酯

  摘要：

  研究了 (E)-1-烯基硼酸频哪醇酯 3 的两种合成路线。1-炔烃 I 与 1,3,2-苯并二恶硼烷（儿茶酚硼烷）的硼氢化反应是在 THF 中的 BH 3 与儿茶酚反应生成的，在 THF 中催化量的二环己基硼烷存在下，室温下进行，得到相应的 (E)-1-烯基硼酸儿茶酚酯 2. 用 2,3-二甲基-2,3-丁二醇 (频哪醇) 处理所得酯 2 容易得到所需产物 3，其对空气、水分和色谱不敏感，整体产量好到高。顺序反应是以一锅方式从THF中的BH 3 到3的高效途径。或者，用 4,4,5,5-四甲基-1,3 对 1 进行硼氢化，2-二氧硼烷（频哪醇硼烷）是在催化量的二环己基硼烷的存在下在室温下在纯净条件下获得的，以良好至极好的产率直接提供相应的产物 3。从充分利用频哪醇硼烷和不使用溶剂的角度来看，该路线非常有效且对环境无害，并且能够使用多种炔烃1，包括官能化的炔烃1，例如HCCCH 2 Cl和HCCCH

  DOI：

  10.1055/s-2004-829165

文献信息

• XBphos-Rh: a halogen-bond assembled supramolecular catalyst
  作者：Lucas Carreras、Marta Serrano-Torné、Piet W. N. M. van Leeuwen、Anton Vidal-Ferran

  DOI：10.1039/c8sc00233a

  日期：——

  pyridyl- and iodotetrafluoroaryl-substituted phosphines were assembled in the presence of a rhodium(I) precursor to form the corresponding halogen-bonded complex XBphos-Rh. The presence of fluorine substituents at the iodo-containing supramolecular motif was not necessary for halogen bonding to occur due to the template effect exerted by the rhodium center during formation of the halogen-bonded complex

  据报道使用卤素键作为构建催化剂主链的工具。具体地，在铑（I）前体的存在下组装吡啶基和碘四氟芳基取代的膦，以形成相应的卤素键合的配合物XBphos-Rh。对于含卤素的超分子基序而言，氟取代基的存在对于卤素键的发生不是必需的，这是由于在卤素键合的配合物形成过程中铑中心发挥了模板作用。卤素键合的超分子配合物已成功地在末端炔烃的催化硼氢化反应中进行了测试。
• Stereoselective Synthesis of Conjugated 2,4-Alkadienoates via the Palladium-Catalyzed Cross-Coupling of 1-Alkenylboronates with 3-Bromo-2-alkenoates
  作者：Teiji Yanagi、Takayuki Oh-e、Norio Miyaura、Akira Suzuki

  DOI：10.1246/bcsj.62.3892

  日期：1989.12

  (2E,4E)-, (2Z,4E)-, and (2E,4Z)-2,4-Alkadienoates can be synthesized in high yields by the cross-coupling of ethyl (E)-3-bromoacrylate, methyl (E)-3-bromo-2-methylpropenoate, ethyl (Z)-3-bromocrotonate,1-bromo-2-(ethoxycarbonyl)cyclohexene, and 4-bromocoumarin with 2-[(E)-1-alkenyl]-1,3,2-benzodioxaboroles or diisopropyl (Z)-1-hexenylboronate in the presence of 3 mol% of Pd(OAc)2, 6 mol% of PPh3, and 2 equivalents of Na2CO3 or K2CO3 in alcoholic solvents while retaining the original configuration of the double bonds in β-bromo esters and 1-alkenylboronates. Although the coupling reaction with 1-hexenylboronate with (Z)-3-bromoacrylate gave a mixture of ethyl (2Z,4E)- and (2E,4E)-nonadienoates in a ratio of 63 : 37, it was found that the use of bis(diphenylphosphino)ferrocene as a ligand of palladium brought about the stereoselective coupling under mild conditions.

  (2E,4E)-、(2Z,4E)- 和 (2E,4Z)-2,4-烷二烯酸酯可以通过乙基(E)-3-溴丙烯酸酯、甲基(E)-3-溴-2-甲基丙烯酸酯、乙基(Z)-3-溴丙烯酸酯、1-溴-2-(乙氧羰基)环己烯和4-溴香豆素与2-[(E)-1-烯基]-1,3,2-苯并二氧硼烷或二异丙基(Z)-1-己烯基硼酸酯在3摩尔%的Pd(OAc)2、6摩尔%的PPh3和2当量的Na2CO3或K2CO3的存在下，在醇溶剂中交叉耦合合成，且保持β-溴酯和1-烯基硼酸酯中双键的原始构型。尽管1-己烯基硼酸酯与(Z)-3-溴丙烯酸酯的耦合反应生成了63:37比率的乙基(2Z,4E)-和(2E,4E)-九烯酸酯的混合物，但发现使用双(苯基磷)铁烯作为钯的配体在温和条件下能够实现立体选择性耦合。
• A CONVENIENT STEREOSPECIFIC SYNTHESIS OF α,β-UNSATURATED CARBOXYLIC ESTERS VIA THE PALLADIUM-CATALYZED CARBONYLATION OF 1-ALKENYLBORANES
  作者：Norio Miyaura、Akira Suzuki

  DOI：10.1246/cl.1981.879

  日期：1981.7.5

  1-Alkenyiboranes readily prepared by the hydroboration of alkynes react smoothly with carbon monoxide in the presence of palladium chloride and sodium acetate in methanol to give the corresponding α,β-unsaturated carboxylic esters with retention of configuration with respect to alkenylboranes in good yields.

  通过烷炔的氢硼化容易制备的1-烯基硼烷在甲醇中与煤气反应，存在氯化铂和醋酸钠，可以顺利生成相应的α,β-不饱和羧酸酯，并保持与烯基硼烷的构象一致，产率良好。
• The palladium-catalyzed “head-to-tail” cross-coupling reaction of 1-alkenylboranes with phenyl or 1-alkenyl iodides. A novel synthesis of 2-phenyl-1-alkenes or 2-alkyl-1,3-alkadienes via organoboranes
  作者：Norio Miyaura、Akira Suzuki

  DOI：10.1016/s0022-328x(00)82970-8

  日期：1981.6

  The reaction of phenyl or 1-alkenyl iodides with 1-alkenyl-1,3,2-benzodioxaboroles readily obtainable via the hydroboration of 1-alkynes, gives the corresponding “head-to-tail” cross-coupling products, 2-phenyl-1-alkenes or 2-alkyl-1,3-alkadienes, in good yields. The reaction is effectively catalyzed by catalytic amounts of palladium compounds in the presence of triethylamine.

  苯基或1-烯基碘化物与1-烯基-1,3,2-苯并二氧杂硼酸的反应可通过1-炔烃的硼氢化反应轻松获得，得到相应的“头对尾”交叉偶联产物2-苯基- 1-烯烃或2-烷基-1,3-链二烯，收率高。在三乙胺的存在下，通过催化量的钯化合物可有效地催化反应。
• The Reactions of Copper(I) 1-Alkenyltrimethylborates with Allylic Bromides or 2-Propynyl Bromide
  作者：Norio Miyaura、Takashi Yano、Akira Suzuki

  DOI：10.1246/bcsj.53.1471

  日期：1980.5

  The reactions between copper(I) 1-alkenyltrimethylborates (readily obtainable from 2-(1-alkenyl)-1,3,2-benzodioxaboroles and methyllithium) and allylic bromides or 2-propynyl bromide were found to give corresponding coupling products. These reactions provide new synthetic routes to 1,4-alkadienes or 1,2,7-alkatrien-5-ynes.

  发现铜 (I) 1-烯基三甲基硼酸盐（可容易地从 2-(1-烯基)-1,3,2-苯并二氧杂环戊烷和甲基锂获得）与烯丙基溴或 2-丙炔基溴之间的反应得到相应的偶联产物。这些反应为 1,4-二烯烃或 1,2,7-烷三烯-5-炔提供了新的合成路线。