Jean-Ho Chu*, Jin Lee, Guan-Wei Liao, Lin-En Zeng, Chien-Wen Lin, Ching-Hung Cheng, Wen-Chieh Lin, Li-Ching Shen, Guo-Feng Chen, Rong Chang and Andrew C.-H. Sue,
{"title":"钯介导的 9(10H)-吖啶酮的位点选择性 C-H 键活化和芳基化及机理研究:化学计量和催化方法","authors":"Jean-Ho Chu*, Jin Lee, Guan-Wei Liao, Lin-En Zeng, Chien-Wen Lin, Ching-Hung Cheng, Wen-Chieh Lin, Li-Ching Shen, Guo-Feng Chen, Rong Chang and Andrew C.-H. Sue, ","doi":"10.1021/acs.organomet.4c0035610.1021/acs.organomet.4c00356","DOIUrl":null,"url":null,"abstract":"<p >Palladium-mediated site-selective C–H bond activations of 9(10<i>H</i>)-acridinone, resulting in the formation of 4- and 1-arylated 9(10<i>H</i>)-acridinones, are presented through the use of both stoichiometric and catalytic experiments. In the stoichiometric reactions, two distinct classes of acridinone palladacycles are generated via C (4)–H and C (1)–H bond activations, with the pyridine and ketone groups serving as the directing group, respectively. The constitutional conformation and thermal stability of these palladacycles were elucidated through both X-ray crystallography and NMR spectroscopy. Additionally, an investigation was conducted into the interconversion of C (4 and 1)–H bond-activated palladacycles in trifluoroacetic acid and acetic acid. During the course of C (1)–H bond arylation, a serendipitous discovery led to the isolation of a chromeno [4,3,<i>2-kl</i>] acridinone compound as a byproduct, showcasing good fluorescence properties. Controlled experiments, kinetic isotope effect study, key palladacycles, and the formation of corresponding products support the proposed mechanisms for these presented reactions. Finally, the pyridinyl group can serve as a removable directing group and can be readily eliminated from both 4- and 1-arylated 9(10<i>H</i>)-acridinones.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00356","citationCount":"0","resultStr":"{\"title\":\"Palladium-Mediated Site-Selective C–H Bond Activation and Arylation of 9(10H)-Acridinone and Mechanistic Investigation: Stoichiometric and Catalytic Approaches\",\"authors\":\"Jean-Ho Chu*, Jin Lee, Guan-Wei Liao, Lin-En Zeng, Chien-Wen Lin, Ching-Hung Cheng, Wen-Chieh Lin, Li-Ching Shen, Guo-Feng Chen, Rong Chang and Andrew C.-H. Sue, \",\"doi\":\"10.1021/acs.organomet.4c0035610.1021/acs.organomet.4c00356\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Palladium-mediated site-selective C–H bond activations of 9(10<i>H</i>)-acridinone, resulting in the formation of 4- and 1-arylated 9(10<i>H</i>)-acridinones, are presented through the use of both stoichiometric and catalytic experiments. In the stoichiometric reactions, two distinct classes of acridinone palladacycles are generated via C (4)–H and C (1)–H bond activations, with the pyridine and ketone groups serving as the directing group, respectively. The constitutional conformation and thermal stability of these palladacycles were elucidated through both X-ray crystallography and NMR spectroscopy. Additionally, an investigation was conducted into the interconversion of C (4 and 1)–H bond-activated palladacycles in trifluoroacetic acid and acetic acid. During the course of C (1)–H bond arylation, a serendipitous discovery led to the isolation of a chromeno [4,3,<i>2-kl</i>] acridinone compound as a byproduct, showcasing good fluorescence properties. Controlled experiments, kinetic isotope effect study, key palladacycles, and the formation of corresponding products support the proposed mechanisms for these presented reactions. Finally, the pyridinyl group can serve as a removable directing group and can be readily eliminated from both 4- and 1-arylated 9(10<i>H</i>)-acridinones.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-10-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00356\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00356\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00356","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
通过使用定量实验和催化实验,介绍了钯介导的 9(10H)-acridinone 的位点选择性 C-H 键活化,从而形成 4-芳基化和 1-芳基化的 9(10H)-acridinones 。在定量反应中,通过 C (4)-H 键和 C (1)-H 键活化生成了两类不同的吖啶酮泛酰环,吡啶和酮基分别作为指导基团。通过 X 射线晶体学和核磁共振波谱分析,阐明了这些帕拉代二环的构象和热稳定性。此外,还研究了三氟乙酸和乙酸中 C (4) 和 1) -H 键活化的泛影葡聚糖的相互转化。在 C (1)-H 键芳基化过程中,一个偶然的发现导致分离出一种色烯[4,3,2-kl]吖啶酮化合物作为副产品,该化合物具有良好的荧光特性。受控实验、动力学同位素效应研究、关键配位环以及相应产物的形成都支持了这些反应的拟议机制。最后,吡啶基可以作为一个可移除的定向基团,并且可以很容易地从 4-芳基化和 1-芳基化的 9(10H)-吖啶酮中消除。
Palladium-Mediated Site-Selective C–H Bond Activation and Arylation of 9(10H)-Acridinone and Mechanistic Investigation: Stoichiometric and Catalytic Approaches
Palladium-mediated site-selective C–H bond activations of 9(10H)-acridinone, resulting in the formation of 4- and 1-arylated 9(10H)-acridinones, are presented through the use of both stoichiometric and catalytic experiments. In the stoichiometric reactions, two distinct classes of acridinone palladacycles are generated via C (4)–H and C (1)–H bond activations, with the pyridine and ketone groups serving as the directing group, respectively. The constitutional conformation and thermal stability of these palladacycles were elucidated through both X-ray crystallography and NMR spectroscopy. Additionally, an investigation was conducted into the interconversion of C (4 and 1)–H bond-activated palladacycles in trifluoroacetic acid and acetic acid. During the course of C (1)–H bond arylation, a serendipitous discovery led to the isolation of a chromeno [4,3,2-kl] acridinone compound as a byproduct, showcasing good fluorescence properties. Controlled experiments, kinetic isotope effect study, key palladacycles, and the formation of corresponding products support the proposed mechanisms for these presented reactions. Finally, the pyridinyl group can serve as a removable directing group and can be readily eliminated from both 4- and 1-arylated 9(10H)-acridinones.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.