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Regioisomerism in Symmetric Dimethyl Dialdehydes Dictates their Photochemical Reactivity
datasetposted on 2022-06-24, 19:08 authored by Florian Feist, Leona L. Rodrigues, Sarah L. Walden, Christopher Barner-Kowollik
We herein report the first light-driven selective monoderivatization (desymmetrization) of two chemically equivalent carbonyl groups in a single chromophore. By comparing of four symmetric regioisomers, featuring two equivalent ortho-methylbenzaldehyde units, we identify dimethyltherephtalaldehydes (DMTAs) which can be activated in a dual wavelength-selective fashion. Under visible light and UV-light irradiation, DMTAs undergo two consecutive Diels–Alder reactions exhibiting near-quantitative endo-selectivity (>99%) and provide excellent yields (96–98%). The influence of the regioisomerism of the dialdehydes on their photochemical behavior is profound, evidenced by an in-depth investigation of their photochemical performance. We exemplify the capability of the photosystems via the synthesis of complex Diels–Alder adducts with various dienophiles, including alkynes.
provide excellent yieldsfour symmetric regioisomersfeaturing two equivalent>- methylbenzaldehyde unitsdriven selective monoderivatizationselective fashionvisible lightvarious dienophilessingle chromophorephotosystems viaphotochemical reactivityphotochemical performancephotochemical behaviorortho light irradiationincluding alkynesherein reportfirst lightendo dual wavelengthdepth investigation