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Unveiling Latent Photoreactivity of Imines
Author(s) -
Uraguchi Daisuke,
Tsuchiya Yuto,
Ohtani Tsuyoshi,
Enomoto Takafumi,
Masaoka Shigeyuki,
Yokogawa Daisuke,
Ooi Takashi
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201913555
Subject(s) - density functional theory , reactivity (psychology) , chemistry , excited state , modularity (biology) , chemical space , complete active space , computational chemistry , photochemistry , physics , drug discovery , atomic physics , basis set , medicine , biochemistry , alternative medicine , pathology , biology , genetics
Unlike carbonyl compounds, it has long been common understanding that excited imines show virtually no photoreactivity, and hence their properties and potential utility in chemical science remain largely unexplored. Now, a strategy is presented for eliciting latent photoreactivity of imines based on the introduction of a donor–acceptor (D‐A) structure to extend the lifetime of their photoexcited states. A series of spectroscopic analyses and density functional theory calculations reveal unique photophysical properties of the D‐A‐type imines. Furthermore, the reactivity of the D‐A‐type imines is demonstrated by using them as a photoredox catalyst for atom‐transfer radical addition. These findings illuminate a previously neglected chemical space in the field of photochemistry, which will be exploited by taking advantage of the inherent structural modularity of imines.