Abstract
In this study, the photosensitive nature of reactive enamine and polyenamine intermediates is investigated to improve our understanding of light-mediated aminocatalytic reactions. Experimental optical absorption data and TD-DFT calculations reveal that these intermediates are excited directly from the HOMO on the enamine moiety to low-lying unoccupied orbitals localized on the catalyst scaffold. This indicates that the photophysical properties of enamine intermediates can be tuned for visible light-mediated reactions by modifications to the aminocatalyst.
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