2026-07-08 岡山大学,東北大学
＜関連情報＞
- https://www.okayama-u.ac.jp/tp/release/release_id1566.html
- https://pubs.acs.org/doi/10.1021/acs.joc.6c00193
O-ニトロベラトリルアミドオキシムからの光誘起によるアミジニルラジカルの生成と水溶液中でのその分子内環化 Photo-triggered Formation of an Amidinyl Radical from O-Nitroveratril Amidoxime and Its Intramolecular Cyclization in Aqueous Media
Hidenori Okamura,Yui Kaneyama,Kenshin Norizuki,Kouki Sakata,Steven William,and Fumi Nagatsug
The Journal of Organic Chemistry Published: June 22, 2026
DOI:https://doi.org/10.1021/acs.joc.6c00193
Abstract
Photochemical reactions compatible with physiological conditions are powerful tools for chemical biology and medicinal chemistry. Herein, we report that 3,4-dimethoxy-o-nitrobenzyl (o-nitroveratril) amidoxime ethers generate amidinyl radicals upon photoirradiation, yielding 6-aminophenanthridines via the intramolecular cyclization of the corresponding biaryl precursors. This photoreaction proceeds under physiologically relevant conditions, specifically in the aqueous buffers, to yield a series of substituted amino-phenanthridines in moderate yields. Mechanistic studies demonstrated that the reaction proceeds through homolytic N–O bond cleavage triggered by the photoexcitation of the o-nitroveratril moiety. Detailed analysis also identified amino-azaspirolactam as a side product, highlighting the bilateral reaction modes of amidoxime-derived radical species. Finally, the photoinduced cyclization was demonstrated within HeLa cells, highlighting its potential for light-induced construction and control of bioactive compounds.
