1-ethyloxabenzonorbornadiene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-ethyloxabenzonorbornadiene
• 英文别名: 1-ethyl-4-hydro-1,4-epoxynaphthalene；(1S,8R)-1-ethyl-11-oxatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraene
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: OZPHHIHQZWRDEV-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-ethyloxabenzonorbornadiene 在 palladium diacetate 、 copper(l) cyanide 、 对甲苯磺酸 作用下， 以 乙醚 为溶剂， 反应 142.0h， 生成 4-butyl-1-ethyl-2-methylnaphthalene
  参考文献：
  名称：

  环丙烷化的7-氧杂苯并降冰片二烯与有机酸盐的1型开环反应

  摘要：

  首次研究了环丙烷化的7-恶唑基降冰片二烯的亲核开环，为制备2-甲基-1,2-二氢萘-1-醇提供了一种新颖的方法。令人满意的产率（高达95％），使用取得Ñ -Bu 2 CuCNLi 2作为亲核试剂和Et 2 O作为溶剂。该反应表明伯，仲，叔和芳族亲核试剂的成功引入，以及带有芳烃取代基和C1-桥头取代基的底物的开环。还提出了这些转换的通用机制。

  DOI：

  10.1021/ol5004737
• 作为产物：
  描述：

  2-乙基呋喃 、 环己-1,3-二烯-5-炔 生成 1-ethyloxabenzonorbornadiene
  参考文献：
  名称：

  铑催化C1-取代7-氧代苯并降冰片二烯与硼酸开环反应的区域选择性研究

  摘要：

  摘要 建立了铑催化C1-取代的氧杂双环烯烃与芳基硼酸开环反应的优化条件，研究了芳基硼酸的作用以及C1取代对氧杂双环烯烃的影响。无论位置如何，带有给电子取代基的芳基硼酸都能以优异的产率提供开环产物，而吸电子取代基更容易受到空间相互作用的影响。尽管可能有两种不同的区域异构体，但发现用芳基硼酸研究的 C1 取代的氧杂双环烯烃的所有铑催化开环反应都具有高度的区域选择性，在所有情况下都得到单一的区域异构体。图形概要

  DOI：

  10.1080/00397911.2014.965330

文献信息

• Regioselective palladium-catalyzed ring-opening reactions of C₁-substituted oxabenzonorbornadienes
  作者：Mohammed Abdul Raheem、Michael Edmunds、William Tam

  DOI：10.1139/cjc-2014-0217

  日期：2014.9

  The effect of ethyl and methoxycarbonyl substitution on the C₁ position of oxabenzonorbornadienes undergoing palladium-catalyzed nucleophilic ring opening was investigated with a variety of aryl iodide nucleophiles. Electron-withdrawing groups in the C₁ position or on the aryl iodide afforded lower yields and led to aromatization of products. The presence of an electron-donating group in either position provided high yields in all cases. Despite variances in electronic nature, all trials produced a single regioisomeric product resulting from addition of the aryl group to the olefin carbon farthest from the C₁ substituent. Based on these findings, a mechanism has also been proposed.

  对氧苯并[2.2.1]辛二烯在钯催化的亲核开环反应中进行乙基和甲氧羰基取代对C₁位置的影响进行了研究，使用各种芳基碘亲核试剂。C₁位置或芳基碘中的电子吸引基团导致产率降低并使产物芳构化。在任一位置存在电子给予基团均提供高产率。尽管电子性质有所不同，所有实验均产生了一个单一的区域异构产物，该产物是芳基与离C₁取代基最远的烯烃碳的加成结果。基于这些发现，还提出了一个机理。
• Synthesis of C1-Substituted Oxabenzonorbornadienes
  作者：William Tam、Jamie Haner、Kelsey Jack、Michelle Menard、Jennifer Howell、Jaipal Nagireddy、Mohammed Raheem

  DOI：10.1055/s-0032-1316686

  日期：2012.9

  Oxabenzonorbornadienes are valuable synthetic intermediates because they can serve as a general template with which to create highly substituted ring systems. However, to date, only very few C1-substituted oxabenzonorbornadienes have been reported. In this study, the synthesis of some C1-substituted oxabenzonorbornadienes was achieved by the Diels-Alder reaction between 2-substituted furans and benzyne. Moderate to good yields (16-80%) of the Diels-Alder reactions were observed. These C1-substituted oxabenzonorbornadienes will find applications as valuable synthetic intermediates and should be useful in studies of transition-metal-catalyzed reactions.
• Synthesis of Cyclopropanated 7-Oxabenzonorbornadienes
  作者：William Tam、Mary McKee、Jamie Haner、Emily Carlson

  DOI：10.1055/s-0033-1340918

  日期：——

  Symmetrical and unsymmetrical 7-oxabenzonorbornadienes have been cyclopropanated using diazomethane gas under palladium catalysis. Good to excellent isolated yields (64-96%) of cyclopropanated oxabenzonorbornadienes were obtained, and excellent stereoselectivities were observed with exo-cyclopropanes as the only stereoisomeric products.
• Type 1 Ring-Opening Reactions of Cyclopropanated 7-Oxabenzonorbornadienes with Organocuprates
  作者：Emily Carlson、Jamie Haner、Mary McKee、William Tam

  DOI：10.1021/ol5004737

  日期：2014.3.21

  For the first time, nucleophilic ring-openings of cyclopropanated 7-oxabenzonorbornadiene were investigated, providing a novel approach to the preparation of 2-methyl-1,2-dihydronaphthalen-1-ols. Satisfactory yields (up to 95%) were achieved using n-Bu2CuCNLi2 as the nucleophile and Et2O as the solvent. The reaction demonstrated successful incorporation of primary, secondary, tertiary and aromatic

  首次研究了环丙烷化的7-恶唑基降冰片二烯的亲核开环，为制备2-甲基-1,2-二氢萘-1-醇提供了一种新颖的方法。令人满意的产率（高达95％），使用取得Ñ -Bu 2 CuCNLi 2作为亲核试剂和Et 2 O作为溶剂。该反应表明伯，仲，叔和芳族亲核试剂的成功引入，以及带有芳烃取代基和C1-桥头取代基的底物的开环。还提出了这些转换的通用机制。
• Study on the Regioselectivity of Rhodium-Catalyzed Ring Opening Reactions of C₁-Substituted 7-Oxabenzonorbornadienes with Boronic Acids
  作者：Michael Edmunds、Michelle L. Menard、William Tam

  DOI：10.1080/00397911.2014.965330

  日期：2015.2.16

  Abstract An optimized condition for the rhodium-catalyzed ring-opening reaction of C1-substituted oxabicyclic alkenes with aryl boronic acids was developed and the effect of aryl boronic acid as well as the effect of C1 substitution on the oxabicyclic alkenes was studied. Aryl boronic acids carrying electron-donating substituents provided the ring-opened products in excellent yields regardless of the

  摘要 建立了铑催化C1-取代的氧杂双环烯烃与芳基硼酸开环反应的优化条件，研究了芳基硼酸的作用以及C1取代对氧杂双环烯烃的影响。无论位置如何，带有给电子取代基的芳基硼酸都能以优异的产率提供开环产物，而吸电子取代基更容易受到空间相互作用的影响。尽管可能有两种不同的区域异构体，但发现用芳基硼酸研究的 C1 取代的氧杂双环烯烃的所有铑催化开环反应都具有高度的区域选择性，在所有情况下都得到单一的区域异构体。图形概要