PhotoCuRiOT · Visible Light-Mediated Copper Photoredox-Catalyzed Ring-Opening Transformations of Activated Small Ring Aza-Heterocycles and Carbacycles

Visible Light-Mediated Copper Photoredox-Catalyzed Ring-Opening Transformations of Activated Small Ring Aza-Heterocycles and Carbacycles

The ever-growing social interest in environmental protection and minimization of energy consumption have instigated the synthetic chemists to look for alternatively activate small organic molecules. Visible-light-mediated photoredox catalysis has been enjoying a renaissance lately. The process harnesses the sustainable solar energy and thus instigate chemical reactions through single-electron transfer or energy transfer events under mild and environmentally benign conditions. Due to their unique and multifarious reactivity profile, visible-light photocatalysts enable challenging yet rewarding bond constructions that are impossible under standard approaches, thereby paving the way towards achieving hitherto inconceivable chemical transformations and broadly impacting the field of organic synthesis, materials science and pharmaceutical chemistry. The primary objectives of PhotoCuRiOT were the demonstration of the concept of visible-light-induced homolysis (VLIH) unambiguously and the development of novel synthetic tactics by photooxidation of small molecules to generate open-shell intermediates that can be productively harnessed for the synthesis of a range of high-value functional motifs. Considering the earth abundance, low cost, and low toxicity, Cu(I/II)-based complexes, especially copper(I/II) phenanthroline derivatives, have been planned to use as efficient photocatalysts instead of commonly-used Ru or Ir-based complexes. The initial plan involved the employment of small ring aza-heterocycles and aminocarbacyles which would supposedly get photooxidized by an in situ generated Cu(II) photocatalyst via VLIH, to generate reactive amino radical cationic intermediates that could undergo successive ring-opening and annulation with suitably functionalized nucleophiles to produce biologically significant cyclic and acyclic nitrogenous organic compounds. PhotoCuRiOT has also aimed to bridge the gap between the fields of medicine and energy by enabling facile and highly selective synthesis of a wide array of high-value organic compounds by utilizing first-row transition metal (e.g. Cu) complexes as environmentally benign photoredox catalysts and visible-light as a sustainable source of energy. The project has achieved most of its objectives and milestones in terms of technical aspects and developments, discovered new directions in earth-abundant metal-complex-based visible-light photocatalysis, and it has fully achieved its parallel objectives regarding the researcher’s training, transfer of knowledge, and fostering his development towards an independent researcher.

Текст от CORDIS, на английски · Данни: CORDIS, © Европейски съюз