The Katayev Research Group has a fundamental interest in developing innovative catalytic strategies, exemplified by photocatalysis, electrochemical synthesis, synergistic, transition metal and organocatalysis, in order to overcome the major challenges of modern organic synthesis. Particularly, a special focus is given on the development of light and electricity driven carbon-hydrogen (C-H) functionalization methodologies of substances, ranging from common feedstocks to complex molecules and materials. This spans but is not limited to the formation of C-C, C-N, and C-O bonds, including asymmetric transformations. The subsequent implementation of such methodologies in the synthesis of natural product, bio relevant compounds and materials is one of the key goals of applied research in our laboratory. We are also engaged in detailed mechanism investigations via physical organic chemistry tools and computational studies, as the understanding of novel catalytic methodologies will lay a foundation for further applications of these novel catalytic concepts, both in academia and industry. Our interest also goes further synthetic work with engineering projects on photoredox and electrochemical flow chemistry for the scalable synthesis of fine chemicals.
Design of Functional Group Transfer Reagents
Design of organic functional group transfer reagents (FGTRs) capable of translating one or even multiple desired functional groups into organic molecule using sustainable catalytic activation pathways stands as an essential need in molecular construction. This concept holds immense potential across various sectors within the field of chemistry. Our group has keen interest in the creation of new reagents and catalytic pathways to access highly functionalized molecules, ensuring atom economy and exclusive selectivity of the process. One of our recent developments lies in the realm of nitration chemistry, a fundamental transformation in organic chemistry. By developing a series of new bench-stable organic nitrating reagents, we were able to enhance the synthesis of nitro derivative molecules beyond the state-of-the-art. Incorporating modern catalytic tools based on visible-light, electricity, and mechanical energy, we create unprecedented and powerful nitration methodologies, while discovering mechanisms and key species of these previously elusive transformations.
Functional Radicals from Inorganic Reagents
The use of earth abundant metals in synergistic catalysis with visible light, electricity or mechanical energy represents a powerful technology to generate functional radicals. Despite the recent novelty of this field, the practical application towards the synthesis of organic molecules remains constrained and inadequately understood in terms of its underlying mechanisms. Leveraging extensive insights in catalysis and radical chemistry, our group is utilizing synergy as a tool to convert inexpensive inorganic compounds into vital functional radicals. We further delve into these mechanistic paradigms by employing number of organic physical chemistry tools available in our group alongside with density functional theory for comprehensive exploration and understanding. One of the representatives is our recent development of cooperative catalysis between iron and catalytic amounts of electron to produce nitryl radicals. The process has proven to be a powerful concept and tolerates a number of chemical transformations for the installation of a nitro group.
Facile Access to Fluorinated Radicals and Beyond
Fluorinated radicals play an important role in the design of new pharmaceutical agents, agrochemicals, and material sciences. Advances in this field have been possible given the availability of various reagents to deliver electrophilic, nucleophilic and ambiphilic RF-radicals. However, the majority of such reagents rely on redox-active scaffolds, requiring intricate engineering and complex synthetic pathways for their accessibility. On the other hand, structurally simple fluorinated carbonyl and sulfur-based compounds exhibit widespread availability in the market, assuming potential utility as viable sources for RF-radicals. Exposing them to photocatalysis and electrochemical synthesis, our group has effectively showcased the considerable potential of these molecules as convenient and cost-effective functional reagents in radical fluorination reactions. By integrating the concept of switchable divergent synthesis, it becomes feasible to explore a wider chemical space of the same radicals, thereby contributing to the achievement of various synthetic targets.