Palladium-Mediated Site-Selective C–H Bond Activation and Arylation of 9(10H)-Acridinone and Mechanistic Investigation: Stoichiometric and Catalytic Approaches
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,
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引用次数: 0
Abstract
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.