2-(2-methylphenyl)-1H-pyrrole-1-carboxylic acid 1,1-dimethylethyl ester | 879904-85-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2-(2-methylphenyl)-1H-pyrrole-1-carboxylic acid 1,1-dimethylethyl ester
• 英文别名: 2-(2'-methylphenyl)pyrrole-1-carboxylic acid tert-butyl ester；1-tert-butoxycarbonyl-2-(2-tolyl)pyrrole；Tert-butyl 2-(2-methylphenyl)pyrrole-1-carboxylate
• CAS: 879904-85-5
• 化学式: C₁₆H₁₉NO₂
• 分子量: 257.332
• InChiKey: MMFBSLLCHPUBMK-UHFFFAOYSA-N

物化性质

• 沸点：
  361.1±40.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  31.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2-methylphenyl)-1H-pyrrole-1-carboxylic acid 1,1-dimethylethyl ester 在 乙二醇 作用下， 反应 0.5h， 以80%的产率得到2-(2-tolyl)pyrrole
  参考文献：
  名称：

  芳基取代的 C3 桥联低聚吡咯作为阴离子受体用于形成超分子有机凝胶

  摘要：

  芳基取代的二吡咯基二酮 (3a-c, 5a-d) 的 BF2 配合物是通过 Suzuki 交叉偶联反应获得的芳基吡咯与丙二酰氯缩合合成的，然后用 BF3.OEt2 处理。CH2Cl2 中各种阴离子（Cl-、Br-、CH3CO2-、H2PO4- 和 HSO4-）的 BF2 复合物 (3a-c) 的结合常数 (Ka11) 以 Ph (3a) > o-tolyl 的顺序降低（ 3b) > 2,6-Me2Ph (3c)，可能是因为结合位点的平面度和相互作用的 o-CH 单元数量不同。正如 CD2Cl2 中的 1H NMR 研究表明的那样，芳基取代的受体表现出与 Cl- 的 [1+1] 结合模式以及在高浓度和低温条件下的 [2+1] 结合模式。这些受体，尤其是苯基取代的 (3a) 和邻甲苯基 (3b)，与 2,6-二甲基苯基 (3c) 和先前报道的衍生物 (1a-c) 相比，由于延长的 pi 共轭，在

  DOI：

  10.1021/ja074435z
• 作为产物：
  描述：

  1-吡咯甲酸叔丁酯 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex sodium hydride 、 碳酸氢钠 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 19.0h， 生成 2-(2-methylphenyl)-1H-pyrrole-1-carboxylic acid 1,1-dimethylethyl ester
  参考文献：
  名称：

  杂环硅烷醇化物与取代的芳基碘化物和溴化物的钯催化交叉偶联反应。

  摘要：

  [反应：见正文]在温和条件下，衍生自多种杂环硅烷醇的硅烷醇钠与各种芳族碘化物和溴化物发生交叉偶联。硅烷醇与甲苯中的等量氢化钠进行原位去质子化反应生成的钠盐在Pd（2）（dba）（3）.CHCl（3）的作用下与碘化物偶合，在室温至50的条件下产率很高芳族溴化物在Pd（I）催化剂12的作用下也与这些盐偶联。

  DOI：

  10.1021/ol053165r

文献信息

• Tri(1-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorus Compounds
  作者：Liye Chen、Peng Ren、Brad P. Carrow

  DOI：10.1021/jacs.6b03215

  日期：2016.5.25

  We report here the remarkable properties of PAd3, a crystalline air-stable solid accessible through a scalable SN1 reaction. Spectroscopic data reveal that PAd3, benefiting from the polarizability inherent to large hydrocarbyl groups, exhibits unexpected electron releasing character that exceeds other alkylphosphines and falls within a range dominated by N-heterocyclic carbenes. Dramatic effects in

  我们在这里报告了 PAd3 的显着特性，PAd3 是一种结晶的空气稳定固体，可通过可扩展的 SN1 反应获得。光谱数据显示，PAd3 受益于大烃基固有的极化性，表现出超出其他烷基膦的意外电子释放特性，并落在以 N-杂环卡宾为主的范围内。在低 Pd 负载下氯（杂）芳烃（40 个例子）的 Suzuki-Miyaura 交叉偶联过程中，PAd3 还具有显着的催化作用，包括商业药物的后期功能化。从氯芳烃合成缬沙坦和啶酰菌胺的工业前体在 10 分钟内具有 ~2 × 10(4) 周转率，证明了卓越的时空产率。
• [EN] TRI-(ADAMANTYL)PHOSPHINES AND APPLICATIONS THEREOF<br/>[FR] TRI-(ADAMANTYL)PHOSPHINES ET LEURS APPLICATIONS
  申请人：UNIV PRINCETON

  公开号：WO2017075581A1

  公开（公告）日：2017-05-04

  In one aspect, phosphine compounds comprising three adamantyl moieties (PAd3) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAd3 ligands are also provided for catalytic synthesis including catalytic cross-coupling reactions.

  在一个方面，本文描述了包括三个金刚烷基团（PAd3）的膦化合物及其相关的合成途径。每个金刚烷基团可以相同也可以不同。例如，连接到磷原子的每个金刚烷基团（Ad）可以独立地从金刚烷、二金刚烷、三金刚烷及其衍生物组成的群体中选择。还提供了包括PAd3配体的过渡金属配合物，用于催化合成，包括催化交叉偶联反应。
• Tri-(adamantyl)phosphines and applications thereof
  申请人：The Trustees of Princeton University

  公开号：US10981157B2

  公开（公告）日：2021-04-20

  In one aspect, phosphine compounds comprising three adamantyl moieties (PAd3) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAd3 ligands are also provided for catalytic synthesis including catalytic cross-coupling reactions.

  一方面，本文描述了包含三个金刚烷基的膦化合物（PAd3）及相关合成路线。每个金刚烷基分子可以相同，也可以不同。例如，连接到磷原子上的每个金刚烷基（Ad）可以独立地选自金刚烷、二金刚烷、三金刚烷及其衍生物组成的组。包含 PAd3 配体的过渡金属配合物还可用于催化合成，包括催化交叉偶联反应。
• Palladium-Catalyzed Cross-Coupling of Five-Membered Heterocyclic Silanolates
  作者：Scott E. Denmark、John D. Baird、Christopher S. Regens

  DOI：10.1021/jo7023784

  日期：2008.2.1

  The preparation of pi-rich 2-aryl heterocycles by palladium-catalyzed cross-coupling of sodium heteroarylsilanolates with aryl iodides, bromides, and chlorides is described. The cross-coupling process was developed through extensive optimization of the following key variables: (1) identification of stable, isolable alkali metal silanolates, (2) identification of conditions for preformation and isolation of silanolate salts, (3) judicious choice in the palladium catalyst/ligand combination, and (4) selection of the protecting group on the nitrogen of indole. It was found that the alkali metal silanolates, either isolated or formed in situ, offered a significant rate enhancement and broader substrate scope over the use of silanols activated by Bronsted bases such as NaOt-Bu. In addition, the optimized conditions for the cross-coupling of 2-indolylsilanolates were readily applied to the cross-coupling of 2-pyrrolyl-, 2-furyl-, and 2-thienylsilanolates.
• Transformation of the Non-Selective Aminocyclohexanol-Based Hsp90 Inhibitor into a Grp94-Seletive Scaffold
  作者：Sanket J. Mishra、Suman Ghosh、Andrew R. Stothert、Chad A. Dickey、Brian S. J. Blagg

  DOI：10.1021/acschembio.6b00747

  日期：2017.1.20

  Glucose regulated protein 94 kDa, Grp94, is the endoplasmic reticulum (ER) localized isoform of heat shock protein 90 (Hsp90) that is responsible for the trafficking and maturation of toll-like receptors, immunoglobulins, and integrins. As a result, Grp94 has emerged as a therapeutic target to disrupt cellular communication, adhesion, and tumor proliferation, potentially with fewer side effects compared to pan- inhibitors of all Hsp90 isoforms. Although, the N-terminal ATP binding site is highly conserved among all four Hsp90 isoforms, recent cocrystal structures of Grp94 have revealed subtle differences between Grp94 and other Hsp90 isoforms that has been exploited for the development of Grp94-selective inhibitors. In the current study, a structure-based approach has been applied to a Grp94 nonselective compound, SNX 2112, which led to the development of 8j (ACO1), a Grp94-selective inhibitor that manifests,similar to 440 nM affinity and >200-fold selectivity against cytosolic Hsp90 isoforms.