2-methyl-3-(2-naphthyl)-2-butene | 13387-51-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-methyl-3-(2-naphthyl)-2-butene
• 英文别名: 2-(3-Methylbut-2-en-2-yl)naphthalene
• CAS: 13387-51-4
• 化学式: C₁₅H₁₆
• 分子量: 196.292
• InChiKey: PJPLQMNQVYETDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  2-methyl-3-(2-naphthyl)-2-butene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以74%的产率得到2,3,3-trimethyl-2-(2-naphthyl)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：

  3-methyl-2-(2-naphthalenyl)-2-butanol 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 0.5h， 以82%的产率得到2-methyl-3-(2-naphthyl)-2-butene
  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

• Single electron transfer-induced cross-coupling reaction of alkenyl halides with aryl Grignard reagents
  作者：Eiji Shirakawa、Ryo Watabe、Takuya Murakami、Tamio Hayashi

  DOI：10.1039/c3cc41923a

  日期：——

  Alkenyl halides were found to undergo coupling with aryl Grignard reagents to give the corresponding styrene derivatives in a stereo-retained manner. The cross-coupling reaction is considered to proceed through a single electron transfer mechanism.

  发现烯基卤化物与芳基格氏试剂偶联，以立体保留的方式得到相应的苯乙烯衍生物。交叉偶联反应被认为是通过单个电子转移机理进行的。
• Dual Intermolecular Allylic C-H Functionalization of the Tetrasubstituted Alkene Scaffold
  作者：Claudio Martínez、Kilian Muñiz

  DOI：10.1002/ejoc.201701624

  日期：2018.3.14

  Simple activation of chloramine‐T by a Brønsted acid generates N‐chlorotosylamide, which serves as a reagent for the selective double C–H functionalization at the allylic position of tetrasubstituted alkenes.

  布朗斯台德酸对氯胺-T的简单活化会生成N-氯代甲苯磺酰胺，可作为四取代烯烃的烯丙基位置处选择性双CH官能化的试剂。
• Lewis Acid Promoted Vicinal Oxytrifluoromethylselenolation of Alkenes
  作者：Yang Li、Shangbiao Zhang、Yanan Wang、Yan Gao、Chao Chen、Zheliang Yuan

  DOI：10.1021/acs.orglett.3c00846

  日期：2023.5.12

  selenoxides as electrophilic trifluoromethylselenolation reagents and alcohols as nucleophiles. With less steric and good nucleophilic solvents (such as ethanol and methol), Tf2O-catalyzed oxytrifluoromethylselenolation could be realized, while stoichiometric Tf2O was required to promote full transformation with less nucleophilic and steric solvents (such as isopropanol and tert-butanol). The reaction featured

  在此，我们使用三氟甲基硒氧化物作为亲电子三氟甲基硒化试剂和醇作为亲核试剂，开发了一种不含金属、路易斯酸促进的烯烃邻位氧三氟甲基硒化反应。使用较少空间和良好亲核溶剂（如乙醇和甲醇），可以实现Tf 2 O 催化的氧三氟甲基硒化，而需要化学计量的 Tf 2 O 以促进与较少亲核和空间溶剂（如异丙醇和叔丁醇）的完全转化-丁醇）。该反应具有良好的底物范围、官能团相容性和非对映选择性。该方法可进一步应用于改性条件下化学计量亲核试剂的氧三氟甲基硒化、氨基三氟甲基硒化。基于初步结果提出了涉及硒离子的机制。
• Newsoroff,G.P.; Sternhell,S., Australian Journal of Chemistry, 1966, vol. 19, p. 1667 - 1675
  作者：Newsoroff,G.P.、Sternhell,S.

  DOI：——

  日期：——