5,6-dihydro-5-(methylsulfonyl)phenanthridine | 92199-83-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 5,6-dihydro-5-(methylsulfonyl)phenanthridine
• 英文别名: 5-(methylsulfonyl)-5,6-dihydrophenanthridine；5-methanesulfonyl-5,6-dihydro-phenanthridine；3-Methansulfonyl-5.6-dihydro-phenanthridin；5-Methansulfonyl-5,6-dihydro-phenanthridin；5-methylsulfonyl-6H-phenanthridine
• CAS: 92199-83-2
• 化学式: C₁₄H₁₃NO₂S
• 分子量: 259.329
• InChiKey: HXKWPTZUQFYYGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5,6-dihydro-5-(methylsulfonyl)phenanthridine 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以92%的产率得到菲啶
  参考文献：
  名称：

  钯催化的亲核取代/ CH活化/芳香化级联反应：一种构建6-未取代的菲啶的方法

  摘要：

  已经开发了一种简便实用的钯催化亲核取代/ CH活化/芳构化级联反应。以现成的N - Ms芳基胺和可商购的2-溴苄基溴衍生物为原料，可以以中等至良好的收率（31-85％）获得一系列6-未取代的菲啶。该协议的潜在应用还通过天然生物碱三香精的快速合成得到了证明。

  DOI：

  10.1021/acs.joc.5b02145
• 作为产物：
  描述：

  2-碘苄胺 在 三乙胺 、 cesium fluoride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 34.0h， 生成 5,6-dihydro-5-(methylsulfonyl)phenanthridine
  参考文献：
  名称：

  Synthesis of Carbazoles and Dibenzofurans via Cross-Coupling of o-Iodoanilines and o-Iodophenols with Silylaryl Triflates

  摘要：

  An efficient route to synthesize a variety of carbazoles and dibenzofurans has been developed. It involves the reaction of o-iodoanilines or o-iodophenols with silylaryl triflates in the presence of CsF to afford the N- or O-arylated products, which are subsequently cyclized using a Pd catalyst to carbazoles and dibenzofurans in good to excellent yields. This chemistry tolerates a variety of functional groups.

  DOI：

  10.1021/ol048564l

文献信息

• Catalytic Direct Arylation with Aryl Chlorides, Bromides, and Iodides:  Intramolecular Studies Leading to New Intermolecular Reactions
  作者：Louis-Charles Campeau、Mathieu Parisien、Annie Jean、Keith Fagnou

  DOI：10.1021/ja055819x

  日期：2006.1.1

  and heterocyclic arenes with aryl iodides, bromides, and chlorides has been developed. These reactions occur in excellent yield and are highly selective. Studies with aryl iodides substrates revealed that catalyst poisoning occurs due to the accumulation of iodide in the reaction media. This can be overcome by the addition of silver salts which also permits these reactions to occur at lower temperature

  已开发出一种用于将多种简单和杂环芳烃与芳基碘化物、溴化物和氯化物进行分子内直接芳基化的催化剂。这些反应以极好的收率发生并且具有高度选择性。对芳基碘化物底物的研究表明，由于碘化物在反应介质中的积累，会发生催化剂中毒。这可以通过添加银盐来克服，银盐也允许这些反应在较低温度下发生。该方法的效用通过咔唑天然产物的快速合成和通过直接芳基化产物的开环反应合成空间位阻四邻位取代的联芳基来说明。机理研究提供了对催化剂的深入了解 s 作用模式并显示在钯催化的简单芳烃的直接芳基化中存在动力学上显着的 CH 键裂解。从这些研究中获得的知识导致了以前无法获得的芳烃的新分子间芳基化反应的发展，为其他新的直接芳基化过程的发展打开了大门。
• High-Yielding Intramolecular Direct Arylation Reactions with Aryl Chlorides
  作者：Louis-Charles Campeau、Praew Thansandote、Keith Fagnou

  DOI：10.1021/ol050501v

  日期：2005.4.1

  [reaction: see text] An N-heterocyclic carbene palladium catalyst system is used to promote direct arylation of a broad range of aryl chlorides to form six- and five-membered ring biaryls. An influence of the halide on the palladium precatalyst on catalyst activation has been revealed, as has a beneficial effect of NHC salts that allows the turnover numbers to be increased by simple addition of imidazolium

  [反应：见正文] N-杂环卡宾钯催化剂体系用于促进多种芳基氯的直接芳基化反应，形成六元和五元环联芳基。已经揭示了卤化物对钯预催化剂对催化剂活化的影响，因为NHC盐具有有益的作用，该作用使得可以通过将咪唑鎓盐简单地添加到反应混合物中来增加周转率。
• Palladium-Catalyzed Regiocontrolled Domino Synthesis of <i>N</i>-Sulfonyl Dihydrophenanthridines and Dihydrodibenzo[<i>c</i>,<i>e</i>]azepines: Control over the Formation of Biaryl Sultams in the Intramolecular Direct Arylation
  作者：Joydev K. Laha、Neetu Dayal、Roli Jain、Ketul Patel

  DOI：10.1021/jo501910q

  日期：2014.11.21

  A palladium-catalyzed domino N-benzylation/intramolecular direct arylation involving sulfonanilides and 2-bromobenzyl bromides has been developed for the first time, providing a workable access to N-sulfonyl dihydrophenanthridines in good to excellent yields. Under the optimized conditions, the formation of 5,6-dihydrophenanthridines was largely controlled over the formation of biaryl sultams containing

  首次开发了包括磺酰苯胺和2-溴苄基溴的钯催化的多米诺骨牌N-苄基化/分子内直接芳基化，提供了以良好至极佳收率的N-磺酰基二氢菲啶的可行途径。在优化的条件下，5，6-二氢菲啶的形成大大地控制了含有七个成员环的联芳基阿马丹的形成。发现优化的条件可扩展至联芳基杜仲形成上的N-磺酰基-6,7-二氢-5 H-二苯并[ c，e ]氮杂的区域控制的多米诺骨形成。使用合适的底物，仅可获得联芳基阿马丹。
• Steric Effect of Carboxylate Ligands on Pd-Catalyzed Intramolecular C(sp² )-H and C(sp³ )-H Arylation Reactions
  作者：Yutaka Tanji、Naoya Mitsutake、Tetsuaki Fujihara、Yasushi Tsuji

  DOI：10.1002/anie.201804566

  日期：2018.8.6

  carboxylic acid bearing three cyclohexylmethyl substituents at the α‐position, namely, tri(cyclohexylmethyl)acetic acid, is demonstrated to act as an efficient ligand source in Pd‐catalyzed intramolecular C(sp2)−H and C(sp3)−H arylation reactions. The reactions proceed smoothly under mild reaction conditions, even at room temperature due to the steric bulk of the carboxylate ligands, which accelerates the

  在α-位置带有三个环己基甲基取代基的大分子羧酸，即三（环己基甲基）乙酸被证明是Pd催化的分子内C（sp 2）-H和C（sp 3）的有效配体来源-H芳基化反应。由于羧酸盐配体的空间体积较大，即使在室温下，反应也可在温和的反应条件下顺利进行，这加快了催化循环中确定C H键活化步骤的速度。
• Synthesis of carbazoles and dibenzofurans via cross-coupling of o-iodoanilines and o-iodophenols with silylaryl triflates and subsequent Pd-catalyzed cyclization
  作者：Zhijian Liu、Richard C. Larock

  DOI：10.1016/j.tet.2006.10.071

  日期：2007.1

  An efficient route to a variety of carbazoles and dibenzofurans has been developed. It involves the reaction of o-iodoanilines or o-iodophenols with silylaryl triflates in the presence of CsF to afford the N- or O-arylated products, which are subsequently cyclized using a Pd catalyst to carbazoles and dibenzofurans in good to excellent yields. By using this methodology, the carbazole alkaloid, mukonine has been synthesized in 76% overall yield in three steps. (c) 2006 Elsevier Ltd. All rights reserved.