methyl 2-methyl-5-(p-tolyl)-4,5-dihydrofuran-3-carboxylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2-methyl-5-(p-tolyl)-4,5-dihydrofuran-3-carboxylate
• 英文别名: methyl 5-methyl-2-(4-methylphenyl)-2,3-dihydrofuran-4-carboxylate
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: FAZYKOQYNFODJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl 2-methyl-5-(p-tolyl)-4,5-dihydrofuran-3-carboxylate 在 copper(ll) bromide 作用下， 以 硝基甲烷 为溶剂， 反应 3.0h， 以85%的产率得到methyl 2-methyl-5-(p-tolyl)furan-3-carboxylate
  参考文献：
  名称：

  通过亲核取代触发的杂芳烃化反应从2-烷氧基-2,3-二氢呋喃合成呋喃和吡咯

  摘要：

  以2-烷氧基-2,3-二氢呋喃为模块前体，开发了一种有效的合成α-官能化呋喃和吡咯衍生物的方法。该协议的特点是以前未报道的串联亲核取代/杂芳构化反应。在酸性催化剂（例如溴化铜和铁）存在下，诸如吲哚，α-氧杂环丁烯二硫缩醛，三甲氧基苯和二甲氧基萘等亲核试剂可以轻松地与2-烷氧基-2,3-二氢呋喃反应，生成α-官能化的五元环杂环。氯化物。还讨论了该反应的机理，其中第一步是亲核取代，是触发随后的杂芳烃化的关键。该方法还可以扩展到二氢噻吩的合成。

  DOI：

  10.1002/adsc.201500993
• 作为产物：
  描述：

  methyl 1-acetyl-2-(p-tolyl)cyclopropanecarboxylate 在 C₅₁H₄₂OP₂Se₂⁽²⁺⁾*2C₃₂H₁₂BF₂₄^(1-) 作用下， 以 1,2-二氯乙烷 为溶剂， 以83 %的产率得到methyl 2-methyl-5-(p-tolyl)-4,5-dihydrofuran-3-carboxylate
  参考文献：
  名称：

  Cloke-Wilson 重排的硫族键合催化

  摘要：

  通常，强路易斯酸、布朗斯台德酸和路易斯碱会促进 Cloke-Wilson 重排。在此，建立了 Cloke-Wilson 重排的硫属键合催化方法，提供中等至良好产率的二氢呋喃。

  DOI：

  10.1002/chem.202203822

文献信息

• Chemodivergent Photocatalytic Synthesis of Dihydrofurans and β,γ‐Unsaturated Ketones
  作者：Arianna Quintavalla、Ruben Veronesi、Davide Carboni、Ada Martinelli、Nelsi Zaccheroni、Liviana Mummolo、Marco Lombardo

  DOI：10.1002/adsc.202100260

  日期：2021.7

  A synthetic procedure, catalysed by Ir(ppy)3 under visible-light irradiation, for the chemodivergent synthesis of 2,3-dihydrofurans (3) or β,γ-unsaturated ketones (7) starting from α-halo ketones (1) and alkenes (2) has been developed. The mild reaction conditions and the redox-neutral nature of the process make it particularly sustainable avoiding the use of both sacrificial reactants and stoichiometric

  在可见光照射下由 Ir(ppy) 3催化的合成方法，用于从 α-卤代酮 ( 1 ) 和2,3-二氢呋喃 ( 3 ) 或 β,γ-不饱和酮 ( 7 )化学发散合成烯烃 ( 2 ) 已被开发。该过程的温和反应条件和氧化还原中性性质使其特别可持续，避免使用牺牲反应物和化学计量强氧化剂。在 DFT 计算的支持下，仔细的实验​​研究允许详细披露可能的机制途径，并将合成化学趋向于3或7，不仅取决于基材的性质，还取决于实验条件的选择。
• Electronic and steric effects in the addition of electrophilic 1,3-dicarbonylalkyl radicals to styrenes
  作者：Enrico Baciocchi、Renzo Ruzziconi

  DOI：10.1021/jo00015a037

  日期：1991.7

  The addition reactions of 1,3-dicarbonylalkyl radicals to ring-substituted styrenes have been kinetically investigated in MeOH and/or MeCN. It has been observed that the rate effect of ring substituents is nearly identical in the reactions of MeCOCHCOMe (1), MeOCOCHCOMe (2) and MeOCOCHCOOMe (4), the rho-value, in MeOH being -0.96, -1.01 and -1.06, respectively. Since the three radicals are relatively strong oxidants and have similar reduction potentials, an important contribution of the charge transfer structure RCOCHCORCH2CHAr.+ to the addition transition state is suggested. It has also be found that in the reactions of 1 and 4 with alpha-alkyl-substituted styrenes the rate of addition is strongly influenced by the nature of the alkyl group, decreasing in the order: Me > Et > (i)Pr > (t)Bu. The observed effects are much larger than those reported for the corresponding reactions of the nucleophilic cyclohexyl radical. It is suggested that the alpha-alkyl substituents exert an effect of steric inhibition of resonance thereby ring delocalization of the charge and/or unpaired electron in the transition state is significantly reduced. Delocalization may be more important in the reactions of 1 and 4 than in those of the cyclohexyl radical since it is possible that the former utilizes a transition state occurring later along the reaction coordinate and/or characterized by a larger extent of charge transfer.
• Iodine-Catalyzed Radical Oxidative Annulation for the Construction of Dihydrofurans and Indolizines
  作者：Shan Tang、Kun Liu、Yue Long、Xinlong Gao、Meng Gao、Aiwen Lei

  DOI：10.1021/acs.orglett.5b00912

  日期：2015.5.15

  Through iodine catalysis, the direct oxidative coupling/annulation of beta-keto esters or 2-pyridinyl-beta-esters with alkenes was achieved. This reaction procedure provides a simple and selective way for the synthesis of dihydrofurans and indolizines in one step.
• Synthesis of Furans and Pyrroles from 2-Alkoxy-2,3-dihydrofurans Through a Nucleophilic Substitution-Triggered Heteroaromatization
  作者：Changhui Liu、Li Zhou、Wenbo Huang、Man Wang、Yanlong Gu

  DOI：10.1002/adsc.201500993

  日期：2016.3.17

  An effective method to synthesize α‐functionalized furan and pyrrole derivatives was developed using 2‐alkoxy‐2,3‐dihydrofurans as modular precursors. This protocol featured a previously unreported tandem nucleophilic substitution/heteroaromatization reaction. Nucleophiles such as indole, α‐oxoketene dithioacetal, trimethoxybenzene, and dimethoxynaphthalene can react readily with 2‐alkoxy‐2,3‐dihydrofurans

  以2-烷氧基-2,3-二氢呋喃为模块前体，开发了一种有效的合成α-官能化呋喃和吡咯衍生物的方法。该协议的特点是以前未报道的串联亲核取代/杂芳构化反应。在酸性催化剂（例如溴化铜和铁）存在下，诸如吲哚，α-氧杂环丁烯二硫缩醛，三甲氧基苯和二甲氧基萘等亲核试剂可以轻松地与2-烷氧基-2,3-二氢呋喃反应，生成α-官能化的五元环杂环。氯化物。还讨论了该反应的机理，其中第一步是亲核取代，是触发随后的杂芳烃化的关键。该方法还可以扩展到二氢噻吩的合成。
• Chalcogen Bonding Catalysis of the Cloke‐Wilson Rearrangement
  作者：Xinglong Yuan、Lintao Bao、Zhiguo Zhao、Yao Wang

  DOI：10.1002/chem.202203822

  日期：——

  Conventionally, the Cloke-Wilson rearrangement is facilitated by strong Lewis acids, Brønsted acids and Lewis bases. Herein, a chalcogen bonding catalysis approach to the Cloke-Wilson rearrangement is established, affording dihydrofurans with moderate to good yields.

  通常，强路易斯酸、布朗斯台德酸和路易斯碱会促进 Cloke-Wilson 重排。在此，建立了 Cloke-Wilson 重排的硫属键合催化方法，提供中等至良好产率的二氢呋喃。