methyl 1,4-epoxy-1,4-dihydronaphthalene-1-carboxylate | 83164-95-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: methyl 1,4-epoxy-1,4-dihydronaphthalene-1-carboxylate
• 英文别名: 1-carbomethoxy-11-oxatricyclo[6.2.1.0^2,7]undeca-2,4,6,9-tetraene；methyl 1,4-epoxynaphthalene-1(4H)-carboxylate；(+/-)-methyl-1,4-dihydro-1,4-epoxynaphthalene-1-carboxylate；methyl 11-oxatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraene-1-carboxylate
• CAS: 83164-95-8
• 化学式: C₁₂H₁₀O₃
• 分子量: 202.21
• InChiKey: UIGDBIZVIJCOFX-UHFFFAOYSA-N

物化性质

• 熔点：
  82-84 °C(Solv: ligroine (8032-32-4))
• 沸点：
  140-150 °C(Press: 0.8 Torr)
• 密度：
  1.332±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  methyl 1,4-epoxy-1,4-dihydronaphthalene-1-carboxylate 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer silver tetrafluoroborate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 26.0h， 以30%的产率得到4-羟基萘-1-羧酸甲酯
  参考文献：
  名称：

  铑催化的氧杂苯并降冰片二烯和氮杂苯并降冰片二烯的不对称环二聚作用：范围和局限性

  摘要：

  阳离子铑（I）催化的氧杂苯并降冰片二烯环二聚反应可一步合成萘[1,2- b ]呋喃环系统，并具有优异的收率和出色的对映选择性。研究了各种Rh（I）催化剂，Ag（I）盐，溶剂和膦配体对反应收率和对映选择性的影响，并研究了该反应与各种恶双环烯的范围和局限性。用氮杂苯并降冰片二烯类似物获得了相似的结果，以优异的产率和优异的对映选择性提供了相应的环二聚产物。

  DOI：

  10.1021/jo7012884
• 作为产物：
  描述：

  2-(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷-2-基)苯酚 在 仲丁基锂 、 N,N-二异丙基乙胺 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 环己烷 为溶剂， 反应 3.5h， 生成 methyl 1,4-epoxy-1,4-dihydronaphthalene-1-carboxylate
  参考文献：
  名称：

  Generation of Arynes via Ate Complexes of Arylboronic Esters with an ortho-Leaving Group

  摘要：

  An efficient method of generating aryne has been achieved by treating ortho-(trifluoromethanesulfonyloxy)arylboronic acid pinacol ester with tert-or sec-butyllithium. Monitoring the reaction by B-11 NMR has indicated that a boron-ate complex formed in situ is the eventual precursor that converts into aryne near room temperature. The prior formation of the ate complex at a low temperature has enabled us to use various arynophiles, including those bearing base-sensitive groups. The ready availability of the aryne precursors and mutual orthogonality in aryne generation with widely used ortho-silylaryl triflate have enhanced the utility of the method.

  DOI：

  10.1021/ol401140d

文献信息

• [EN] BORONIC ACID DERIVATIVES<br/>[FR] DÉRIVÉS D'ACIDE BORONIQUE
  申请人：MERCK PATENT GMBH

  公开号：WO2019038250A1

  公开（公告）日：2019-02-28

  The present invention relates to a-amino boronic acid derivatives. These compounds are useful for inhibiting the activity of immunoproteasome (LMP7) and for the treatment and/or prevention of medical contidions affected by immunoproteasome activity such as inflammatory and autoimmune diseases, neurodegenerative diseases, proliferative diseases and cancer.

  本发明涉及α-氨基硼酸衍生物。这些化合物对抑制免疫蛋白酶体(LMP7)的活性以及治疗和/或预防受免疫蛋白酶体活性影响的医疗状况，如炎症性和自身免疫疾病、神经退行性疾病、增殖性疾病和癌症，具有用处。
• Iridium-catalyzed ring-opening reactions of unsymmetrical oxabenzonorbornadienes with water and alcohol nucleophiles
  作者：Jarvis Hill、Christopher Wicks、Austin Pounder、William Tam

  DOI：10.1016/j.tetlet.2019.150990

  日期：2019.8

  The iridium-catalyzed ring-opening reaction of unsymmetrical oxabenzonorbornadienes (OBD) with water and alcohol nucleophiles is reported, with the effects of various C1-substituents explored. Electron-donating alkyl groups lead entirely to the substituted naphthol derivatives in excellent yields while substitution of the C1 position for electron-withdrawing groups afforded ring-opened products in

  报道了铱催化的不对称氧杂苯并降冰片二烯（OBD）与水和醇亲核试剂的开环反应，并探索了各种C 1-取代基的作用。给电子的烷基以极好的收率完全导致取代的萘酚衍生物，而用C 1位置取代吸电子基团以合理的收率提供了开环产物，并具有极好的区域选择性。已证明该反应对C 2位置具有高度区域选择性，在所有情况下均未观察到C 3区域异构体。已经包括了用于形成C 2区域异构的开环产物的机制。
• Generation of Arynes Using Trimethylsilylmethyl Grignard Reagent for Activation of <i>ortho</i>-Iodoaryl or <i>ortho</i>-Sulfinylaryl Triflates
  作者：Suguru Yoshida、Keisuke Uchida、Takamitsu Hosoya

  DOI：10.1246/cl.150060

  日期：2015.5.5

  The trimethylsilylmethyl Grignard reagent triggered efficient generation of arynes from various ortho-iodoaryl or ortho-sulfinylaryl triflates. The moderate nucleophilicity and basicity of the reagent facilitated efficient reactions between the aryne precursors and arynophiles containing organometallic nucleophile-sensitive functionalities.

  三甲基硅甲基格氏试剂触发了多种邻碘芳基或邻亚砜芳基三氟甲磺酸酯生成氮烯的高效过程。该试剂适度的亲核性和碱性促进了氮烯前体与含金属有机亲核敏感功能的氮烯受体之间的高效反应。
• Alkynyl Halides in Ruthenium(II)-Catalyzed [2+2] Cycloadditions of Bicyclic Alkenes
  作者：Anna Allen、Karine Villeneuve、Neil Cockburn、Elisabeth Fatila、Nicole Riddell、William Tam

  DOI：10.1002/ejoc.200800424

  日期：2008.8

  Ru-catalyzed [2+2] cycloadditions between bicyclic alkenes and alkynyl halides were found to occur in moderate to good yields. The presence of the halide moiety greatly enhances the reactivity of the alkyne component in the cycloaddition and can be transformed into a variety of products that are difficult or impossible to obtain by direct cycloaddition. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  发现双环烯烃和炔基卤化物之间的 Ru 催化的 [2+2] 环加成以中等至良好的产率发生。卤化物部分的存在极大地增强了炔烃组分在环加成中的反应性，并且可以转化为各种难以或不可能通过直接环加成获得的产物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Ruthenium-Catalyzed Isomerization of Oxa/Azabicyclic Alkenes:  an Expedient Route for the Synthesis of 1,2-Naphthalene Oxides and Imines
  作者：Karine Villeneuve、William Tam

  DOI：10.1021/ja058621l

  日期：2006.3.1

  1,2-Naphthalene oxides and imines can be rapidly accessed through a ruthenium-catalyzed isomerization of readily available 7-oxa/azabenzonorbornadienes. These mild reaction conditions were found to be tolerant to various functional groups and the isomerization is highly regioselective.

  1,2-萘氧化物和亚胺可以通过容易获得的 7-氧杂/氮杂苯并降冰片二烯的钌催化异构化快速获得。发现这些温和的反应条件可以耐受各种官能团，并且异构化具有高度的区域选择性。