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Mechanochemistry-Directed Ligand Design: Development of a High-Performance Phosphine Ligand for Palladium-Catalyzed Mechanochemical Organoboron Cross-Coupling
| Title: | Mechanochemistry-Directed Ligand Design: Development of a High-Performance Phosphine Ligand for Palladium-Catalyzed Mechanochemical Organoboron Cross-Coupling |
| Authors: | Seo, Tamae Browse this author | | Kubota, Koji Browse this author | | Ito, Hajime Browse this author →KAKEN DB |
| Issue Date: | 29-Mar-2023 |
| Publisher: | American Chemical Society |
| Journal Title: | Journal of the American Chemical Society |
| Volume: | 145 |
| Issue: | 12 |
| Start Page: | 6823 |
| End Page: | 6837 |
| Publisher DOI: | 10.1021/jacs.2c13543 |
| Abstract: | Mechanochemical synthesis that uses transition -metal catalysts has attracted significant attention due to its numerous advantages, including low solvent waste, short reaction times, and the avoidance of problems associated with the low solubility of starting materials. However, even though the mechanochemical reaction environment is largely different from that of homogeneous solution systems, transition-metal catalysts, which were originally developed for use in solution, have been used directly in mechanochemical reactions without any molecular-level modifications to ensure their suitability for mechanochemistry. Alas, this has limited the development of more efficient mechanochemical cross-coupling processes. Here, we report a conceptually distinct approach, whereby a mechanochemistry-directed design is used to develop ligands for mechanochemical Suzuki-Miyaura cross-coupling reactions. The ligand development was guided by the experimental observation of catalyst deactivation via the aggregation of palladium species, a problem that is particularly prominent in solid-state reactions. By embedding the ligand into a poly(ethylene glycol) (PEG) polymer, we found that phosphine-ligated palladium(0) species could be immobilized in the fluid phase created by the PEG chains, preventing the physical mixing of the catalyst into the crystalline solid phase and thus undesired catalyst deactivation. This catalytic system showed high catalytic activity in reactions of polyaromatic substrates close to room temperature. These substrates usually require elevated temperatures to be reactive in the presence of catalyst systems with conventional ligands such as SPhos. The present study hence provides important insights for the design of high-performance catalysts for solid-state reactions and has the potential to inspire the development of industrially attractive, almost solvent-free mechanochemical cross-coupling technologies. |
| Rights: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-PVEXQGQTZMQQ8Z8ZHMJJ. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/91259 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 久保田 浩司
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