2026-07-02 大阪大学
図. ガリウム（Ga）(I)錯体上で進行するヨウ化アリールの光誘起酸化的付加反応
＜関連情報＞
- https://resou.osaka-u.ac.jp/ja/research/2026/20260702_1
- https://pubs.acs.org/doi/10.1021/jacs.6c08303
光誘起不均化反応により、ガリウム(I)中心へのアリールヨウ化物の酸化的付加が可能になる Photoinduced Disproportionation Enables Oxidative Addition of Aryl Iodides at a Gallium(I) Center
Nijito Mukai,Sota Iwasaki,Manaya Kawasaki,Ryohei Kishi,Manabu Abe,Takuya Kodama,and Mamoru Tobisu
Journal of the American Chemical Society Published: July 2, 2026
DOI:https://doi.org/10.1021/jacs.6c08303
Abstract
Oxidative addition at transition metals underpins modern cross-coupling reactions but remains largely unrealized at main-group centers for aryl halides. Here, we show that photoinduced disproportionation can serve as an enabling strategy for such transformations. Visible light promotes the oxidative addition of aryl iodides to a Ga(I) metallylene, providing, to our knowledge, the first example of aryl C–I activation at a group 13 center. Mechanistic studies suggest that this transformation is not consistent with direct excited-state reactivity with the Ga(I) complex. Instead, photoexcitation generates a triplet state of gallylene that undergoes intermolecular electron transfer with ground-state gallylene, triggering disproportionation to a reactive radical ion pair. This radical ion-pair manifold, which is enabled by ligand-centered redox ambivalence, provides a viable pathway to bond activation. These findings suggest that photoinduced disproportionation could represent a distinct activation mode for achieving transition-metal-like oxidative addition at main-group elements.
