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Development of New Methods for Visible Light-Induced Activation of C-I, C-O, and S-O Bonds
thesisposted on 01.08.2019 by Maxim Ratushnyy
In order to distinguish essays and pre-prints from academic theses, we have a separate category. These are often much longer text based documents than a paper.
This thesis consists of three parts. The first part describes the development of the mild, visible light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade reaction of vinyl iodides. The method features a formation of previously unknown vinyl hybrid palladium-radical intermediates, capable of a 1,5-HAT process. Overall, the transformation leads to the formation of iodomethyl carbo- and heterocyclic products. The second part of this thesis communicates the development of visible light-induced sulfonylation reaction of vinylarenes with arylsulfonate phenol esters. This protocol operates via new mode of the S−O bond activation, thus constituting a novel reactivity of readily available arylsulfonate esters. The transformation leads to a variety aromatic vinyl sulfones in efficient manner. The third part describes the development of visible light-induced palladium-catalyzed intramolecular C(sp2)−X/C(sp3)−H coupling reaction of aryl triflates leading to a variety of 3,3-di- and 3-monosubstituted oxindole motifs. This method illustrates the first example of the visible light-induced palladium-catalyzed activation of C−O bond leading to the aryl hybrid palladium-radical intermediates. This transformation substantially expands the inventory of organic electrophilic partners for the visible light palladium catalysis.