(E)-2-(but-2-en-2-yl)naphthalene | 74357-40-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (E)-2-(but-2-en-2-yl)naphthalene
• 英文别名: 2-(but-2-en-2-yl)naphthalene；2-[(E)-but-2-en-2-yl]naphthalene
• CAS: 74357-40-7
• 化学式: C₁₄H₁₄
• 分子量: 182.265
• InChiKey: MCUIRWHTLGGZSY-QDEBKDIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (E)-2-(but-2-en-2-yl)naphthalene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以75%的产率得到2,3-dimethyl-2-(naphthalen-2-yl)oxirane
  参考文献：
  名称：

  Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones

  摘要：

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.

  DOI：

  10.1021/jo970743b
• 作为产物：
  描述：

  2-萘甲醇,a-乙基-a-甲基- 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 0.5h， 以76%的产率得到(E)-2-(but-2-en-2-yl)naphthalene
  参考文献：
  名称：

  Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones

  摘要：

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.

  DOI：

  10.1021/jo970743b

文献信息

• Facile Pd(II)- and Ni(II)-Catalyzed Isomerization of Terminal Alkenes into 2-Alkenes
  作者：Hwan Jung Lim、Craig R. Smith、T. V. RajanBabu

  DOI：10.1021/jo900180p

  日期：2009.6.19

  of [(allyl)PdCl]2 or [(allyl)NiBr]2, a triarylphosphine, and silver triflate at room temperature. The isomeric ratio (E:Z) depends on the alkenes, the E-isomer being the major one. The reaction is tolerant to a wide variety of functional groups including other reactive olefins. Unlike the more reactive Ir catalysts, monosubstituted alkenes give almost exclusively the 2-alkenes. Direct comparison to two

  通过用催化量的 [(烯丙基)PdCl] 2或 [(烯丙基)NiBr] 处理单取代和 2,2'-二取代末端烯烃，可以将其异构化为更稳定的内 ( Z )- 和 ( E )-烯烃2 、室温下的三芳基膦和三氟甲磺酸银。异构体比例 ( E : Z ) 取决于烯烃，其中E异构体是主要异构体。该反应可耐受多种官能团，包括其他反应性烯烃。与活性更高的 Ir 催化剂不同，单取代烯烃几乎只生成 2-烯烃。还描述了与该过程中两种最著名的催化剂[Ir(PCy 3 ) 3 ] + [BPh 4 ] -和格拉布第二代复分解催化剂}的直接比较。
• Asymmetric Total Synthesis of (−)-Juvabione via Sequential Ir-Catalyzed Hydrogenations
  作者：Jia Zheng、Cristiana Margarita、Suppachai Krajangsri、Pher G. Andersson

  DOI：10.1021/acs.orglett.8b02405

  日期：2018.9.21

  centers via sequential Ir-catalyzed hydrogenations. The first center is generated by hydrogenation of a styrene-type double bond (99% ee). The successive monohydrogenation of a diene intermediate constitutes the key step, granting high levels of regio- and stereocontrol (94:6 dr). This novel strategy allowed the preparation of (−)-juvabione from simple starting materials in 9 steps and 17% total yield.

  （-）-丁香酮是一种天然的倍半萜烯，具有幼虫的昆虫激素活性，是通过连续的Ir催化的加氢反应构建两个相邻的立体异构中心而合成的。第一中心是通过苯乙烯型双键（99％ee）的氢化而产生的。二烯中间体的连续单氢化是关键步骤，可实现高水平的区域控制和立体控制（94：6 dr）。这种新颖的策略允许从简单的起始原料以9个步骤制备（-）-泛香酮，总收率为17％。
• Highly Stereoselective Positional Isomerization of Styrenes <i>via</i> <scp>Acid‐Catalyzed</scp> Carbocation Mechanism
  作者：Xiao‐Si Hu、Jun‐Xiong He、Ying Zhang、Jian Zhou、Jin‐Sheng Yu

  DOI：10.1002/cjoc.202100218

  日期：2021.8

  The first transition metal-free highly stereoselective positional isomerization of various α-alkyl styrenes through a carbocation mechanism triggered strategy is developed by using Al(OTf)3 as a hidden Brønsted acid catalyst, which provides facile access to value-added acyclic tri- and tetra-substituted alkenes in good yields with high stereoselectivity under mild conditions. The practicality of this

  通过使用 Al(OTf) 3作为隐藏的 Brønsted 酸催化剂，通过碳阳离子机制触发的策略开发了第一个无过渡金属的各种 α-烷基苯乙烯的高度立体选择性位置异构化，这为获得增值的无环三-和在温和条件下以高立体选择性和高收率制备四取代烯烃。该协议的实用性由克级合成、高立体选择性、良好的官能团耐受性和简单的操作进一步突出。机理研究支持 Al(OTf) 3充当隐藏的布朗斯台德酸催化剂并形成碳正离子中间体。
• Titanocene(III)‐Catalyzed Precision Deuteration of Epoxides
  作者：Dina Schwarz G. Henriques、Elena Rojo‐Wiechel、Sven Klare、Regine Mika、Sebastian Höthker、Jonathan H. Schacht、Niklas Schmickler、Andreas Gansäuer

  DOI：10.1002/anie.202114198

  日期：2022.2

  Titanocene catalysis delivers D to the more substituted C-atom of epoxides with high efficiency, deuterium incorporation, and stereoselectivity. A novel method of catalyst activation that prevents isotope scrambling warrants the excellent performance of the reaction.

  二茂钛催化将 D 传递至环氧化物中取代较多的 C 原子，具有高效率、氘并入和立体选择性。一种防止同位素扰乱的催化剂活化新方法保证了反应的优异性能。
• The Reactivity of Radical Anions Generated by Electron-transfer Reaction of Allyl Acetates
  作者：Kazuo Tsujimoto、Yojiro Kamiyama、Yuji Furukawa、Mamoru Ohashi

  DOI：10.1246/bcsj.56.351

  日期：1983.1

  Photoinduced electron-transfer reactions of 3-(2-naphthyl)-2-butenyl acetate gave the reduced products, while the electrochemical and Birch reduction of the acetate furnished (E)-2-(2-naphthyl)-2-butene as the sole product. One-electron reduction was suggested by mechanistic studies of the photoreaction on the basis of deuterium incorporation into the products. A similar mechanism can operate in the

  3-(2-萘基)-2-丁烯基乙酸酯的光致电子转移反应得到还原产物，而乙酸盐的电化学和 Birch 还原提供 (E)-2-(2-萘基)-2-丁烯作为唯一的产品。基于氘掺入产物的光反应机理研究表明了单电子还原。类似的机制可以在醋酸肉桂酯的光还原中起作用。