Publicly Offered Research
Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
Transition-metal-catalyzed C-H bond activation is of much interest, but simple arenes are difficult substrates. I plan a hybrid strategy for the C-H functionalization of simple arenes: catalytic activation of an arene substrate by pi-coordination, which decrease the electron density and enables smooth and selective transition-metal-catalyzed functionalization.
The purpose of this research is the development of a hybrid strategy for C-H functionalization of simple arenes: activation of an arene substrate by catalytic pi-coordination to a metal such as Cr, causing a strong decrease in electron density on the arene, and thus increasing the reactivity towards nucleophilic attack of a reagent or electron-rich metal catalyst.During FY2021, we found that this strategy can be used for the borylation of simple arenes such as toluene, xylene, etc. with bis(pinacolato)diboron in the presence of a base, without the requirement of a transition metal catalyst. The arene is activated by transient ligand exchange with a chromium naphthalene complex, and the reaction does not proceed at all without this activation. While the ligand exchange proceeded smoothly, at the moment the reaction is not catalytic with regard to the chromium complex. Mechanistic studies through experiment and calculation revealed that the reaction proceeds through nucleophilic attack of a borate species.We also found that a similar strategy can be used for the activation of aryl chlorides, resulting in reaction with an arene such as benzene through a radical mechanism. Thus, a aryl chloride coordinated to chromium carbonyl reacted with a solvent amount of arene in the presence of an alcoxide and a bipyridine ligand to produce the biaryl coupling product.
令和3年度が最終年度であるため、記入しない。
All 2022 2021 2020 Other
All Int'l Joint Research (2 results) Journal Article (10 results) (of which Int'l Joint Research: 1 results, Peer Reviewed: 9 results, Open Access: 4 results) Presentation (22 results) (of which Int'l Joint Research: 7 results, Invited: 8 results) Book (1 results) Remarks (1 results)
Chemistry Letters
Volume: 51 Issue: 1 Pages: 38-40
10.1246/cl.210546
130008137567
Science
Volume: 375 Issue: 6581 Pages: 658-663
10.1126/science.abm7599
Communications Chemistry
Volume: 4 Issue: 1 Pages: 76-76
10.1038/s42004-021-00513-2
ACS Catalysis
Volume: 11 Issue: 10 Pages: 5968-5973
10.1021/acscatal.1c01206
Nature Catalysis
Volume: 4 Issue: 7 Pages: 631-638
10.1038/s41929-021-00653-7
Synthesis
Volume: 53 Issue: 18 Pages: 3180-3192
10.1055/a-1478-7061
Bulletin of the Chemical Society of Japan
Volume: 94 Issue: 2 Pages: 404-417
10.1246/bcsj.20200349
130007995387
Journal of the American Chemical Society
Volume: 142 Issue: 10 Pages: 4883-4891
10.1021/jacs.0c00127
Volume: 49 Issue: 11 Pages: 1386-1393
10.1246/cl.200540
130007936944
Asian Journal of Organic Chemistry
Volume: 9 Issue: 3 Pages: 324-325
10.1002/ajoc.202000111
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