研究者情報 | 神奈川大学

イワクラ　イズミ Iwakura Izumi 岩倉　いずみ所属神奈川大学化学生命学部応用化学科神奈川大学大学院工学研究科工学専攻（応用化学領域）職種教授
言語種別	英語
発行・発表の年月	2024/04
形態種別	学術雑誌
標題	Alpha-substituent effect on the photodeprotection of 4,5-dimethoxy-2-nitrobenzyl acetate.
執筆形態	共著
掲載誌名	Chemical Physics
掲載区分	国外
出版社・発行元	ELSEVIER
巻・号・頁	580,pp.112237 (7P)
担当区分	責任著者
国際共著	国際共著
著者・共著者	Sena Hashimoto, _{Izumi Iwakura*}, Yuta Aoki, Atsushi Yabushita, Naomichi Okamura, Noriko Chikaraishi Kasuga, Kazuo Yamaguchi
概要	Since the first report of caged ATP, o-nitrobenzyl groups have been widely used as photolabile protecting groups, and analogue compounds have been used to study hydrogen abstraction. In this work, a caged compound containing acetic acid was used to directly analyse the multiple steps of the deprotection, with the aim of elucidating how and during which steps the α-substituent effect occurs. UV pump-visible probe spectroscopy was used to observe the ultrafast generation of biradicals and zwitterions as reaction intermediates. These experimental results and the results of DFT calculations suggested that the reaction proceeded in the four steps. During the H abstraction reaction, the small α-substituent volume results in a small energy gap between the S^(n-π) and ground states and thus a fast rate of H abstraction. Conversely, during the cyclization reaction, the small α-substituent volume results in a high activation energy and thus a slow rate of cyclization.
DOI	https://doi.org/10.1016/j.chemphys.2024.112237
researchmap用URL	https://www.sciencedirect.com/science/article/pii/S0301010424000661