methyl 2-(2-methoxyphenyl)-2-phenylacetate | 1334532-07-8

• 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-(2-methoxyphenyl)-2-phenylacetate
• CAS: 1334532-07-8
• 化学式: C₁₆H₁₆O₃
• 分子量: 256.301
• InChiKey: PLNJHVVHUFYSJB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.0
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  2-甲氧基苯乙酸甲酯 在 [Rh(OH)(cod)]2 、 4-乙酰氨基苯磺酰叠氮 、 potassium tert-butylate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲基叔丁基醚 、 乙腈 为溶剂， 反应 4.0h， 生成 methyl 2-(2-methoxyphenyl)-2-phenylacetate
  参考文献：
  名称：

  Rhodium-Catalyzed Cross-Coupling Reaction of Arylboronates and Diazoesters and Tandem Alkylation Reaction for the Synthesis of Quaternary α,α-Heterodiaryl Carboxylic Esters

  摘要：

  A rhodium-catalyzed one-pot three-component coupling reaction was developed for the synthesis of quaternary alpha,alpha-heterodiaryl carboxylic esters. This reaction involves cross-coupling of the arylrhodium(I) complexes with alpha-aryldiazoacetates to form oxa-pi-allylrhodium complexes. With KOfBu and alkyl halides, tandem alkylation of the allyl complex occurs to form a quaternary stereocenter at the carbenic carbon.

  DOI：

  10.1021/ol2022577

文献信息

• Brønsted acid-catalyzed Friedel-Crafts-type alkylation of arenes with α-aryl diazoacetates
  作者：Wenming Chen、Guifang Chen、Biao Wang、Wei Wang、Wei Huang、Xu Tian

  DOI：10.1016/j.tetlet.2020.152751

  日期：2021.3

  An efficient Brønsted acid-catalyzed Friedel-Crafts-type alkylation of arenes with α-aryl diazoacetates has been developed. This protocol enables effective access to various highly functionalized diarylmethane derivatives in moderate to high yields. Moreover, the product of selected diaryl acetate could be transformed to β, β-diaryl substituted γ-butyrolactone.

  已经开发了α-芳基重氮乙酸酯对芳烃的有效布朗斯台德酸催化的弗瑞德-克来福特型烷基化。该协议能够以中等到高收率有效地获得各种高度官能化的二芳基甲烷衍生物。而且，所选择的乙酸二芳基酯的产物可以转化为β，β-二芳基取代的γ-丁内酯。
• (C ₆ F ₅ ) ₃ B Catalyzed Chemoselective and <i>ortho</i> ‐Selective Substitution of Phenols with α‐Aryl α‐Diazoesters
  作者：Zhunzhun Yu、Yongfeng Li、Jiameng Shi、Ben Ma、Lu Liu、Junliang Zhang

  DOI：10.1002/anie.201608937

  日期：2016.11.14

  The development of an efficient method for the site‐selective substitution of unprotected phenols has long been considered as an attractive but challenging task. Herein, we describe a highly chemo‐ and ortho‐selective substitution reaction of phenols with α‐aryl α‐diazoacetates with commercially available (C6F5)3B as the catalyst. This reaction proceeds under simple and mild conditions with high efficiency

  长期以来，人们一直认为开发一种有效的方法来对未保护的酚进行位点选择性取代是一项有吸引力的任务，但具有挑战性。本文中，我们描述了苯酚与α-芳基α-重氮乙酸酯的高度化学和邻位选择性取代反应，并以市售（C 6 F 5）3 B作为催化剂。该反应在简单温和的条件下以高效率进行，它具有广泛的底物范围，并且易于扩大规模。
• RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes
  作者：Zhen Liu、Ying Xia、Sheng Feng、Shuai Wang、Di Qiu、Yan Zhang、Jianbo Wang

  DOI：10.1071/ch15218

  日期：——

  A RhI-catalyzed cross-coupling of diazoester with arylstannane was developed. This reaction represents the first Stille-type coupling that uses a diazo compound as the coupling partner. The reaction is operationally simple and can be carried out under mild conditions, thus providing an alternative approach for the synthesis of α-aryl esters. RhI–carbene migratory insertion process is suggested to be involved as the key step in this Stille-type coupling.

  研究人员开发了一种 RhI 催化的重氮酯与芳基锡烷的交叉偶联反应。该反应是首个使用重氮化合物作为偶联剂的 Stille 型偶联反应。该反应操作简单，可在温和的条件下进行，从而为 α 芳基酯的合成提供了另一种方法。据推测，RhI-羰基迁移插入过程是这一斯蒂尔型偶联反应的关键步骤。
• Mechanistic Insights into the Chemo- and Regio-Selective B(C₆F₅)₃ Catalyzed C–H Functionalization of Phenols with Diazoesters
  作者：Qi Zhang、Xiao-Fei Zhang、Mo Li、Cheng Li、Jia-Qin Liu、Yuan-Ye Jiang、Xin Ji、Lu Liu、Yu-Cheng Wu

  DOI：10.1021/acs.joc.9b02035

  日期：2019.11.15

  is reduced via the electron-withdrawing B(C6F5)3. The ortho-selectivity resulted from the greater ortho-C-C (than para-C-C) interaction and the O-H···O and O-H···F hydrogen-bond interaction during electrophilic attack. The greater C-C (than C-O) interaction and the π-π stacking between the benzene rings of phenol and diazoester concerted contribute to the chemo-selective C-H alkylation.

  最近证明了路易斯酸性B（C6F5）3可有效地使苯酚与重氮酯进行CH烷基化。该方法避免了过渡金属催化中一般的羟基活化。不管潜在的对位选择性CH烷基化和OH烷基化如何，都会发生邻位选择性CH烷基化。在本研究中，进行了理论计算以阐明反应机理以及化学和区域选择性的起源。发现先前提出的涉及B（ ）3 / N或B（ ）3 / C的键合机理并不理想，而更受欢迎的是涉及B（ ）3 /C═O键合，速率确定N2消除，确定选择性的亲电攻击和质子转移步骤。同时，新机制与KIE和竞争实验相吻合。该机制的便利性归因于两个因素。首先，B（ ）3 /C═O键可减少亲电子攻击过程中的空间位阻。第二，键合形成共轭体系，通过该体系通过吸电子B（ ）3降低LUMO能量。邻位选择性的原因是亲电子攻击过程中邻位CC（比对位CC）的相互作用更大，以及OH··O和OH··F氢键相互作用。更大的CC（比CO）