Development of solid-state C-H functionalization/photoredox reactions

2023 Fiscal Year Final Research Report

• Project/Area Number: 22K20523
• Research Category: Grant-in-Aid for Research Activity Start-up
• Allocation Type: Multi-year Fund
• Review Section: 0501:Physical chemistry, functional solid state chemistry, organic chemistry, polymers, organic materials, biomolecular chemistry, and related fields
• Research Institution: Hokkaido University
• Principal Investigator: Isshiki Ryota 北海道大学, 化学反応創成研究拠点, 特任助教 (70965227)
• Project Period (FY): 2022-08-31 – 2024-03-31
• Keywords: カップリング反応 / 固体反応 / メカノケミストリー / 光反応 / ラジカル反応

Outline of Final Research Achievements

In recent years, solid-state organic synthesis using a ball mill apparatus has attracted much attention. However, the field is still in its infancy and there are few examples of applicable reactions.
In this study, as a foothold for the establishment of solid-state photoredox reactions, we attempted the solid-state reaction of oxidative ring-opening fluorination reactions to investigate the behavior of radical species in solids. As a result, we found that alkyl radical reactive species, which are unstable in solution under air, can be handled stably under air. We also found that reductive coupling reactions using nickel and photoredox co-catalysts proceeded efficiently.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

固体フォトレドックス反応の開発を志向し、環状アルコールの酸化的開裂を伴うフッ素化反応の固体反応化、ニッケル、光触媒を用いた還元的カップリング反応の固体反応化に成功した。この研究を通して、固体反応化することで溶液中では空気下不安定なラジカル種を不活性ガスを使用せずに安定に取り扱えることを見出した。本反応により不溶性化合物の化学修飾、空気下での反応、反応時間の短縮といった様々な利点があることを明らかにした。