AUTHOR=Budnikova Yulia H. , Dolengovsky Egor L. , Tarasov Maxim V. , Gryaznova Tatyana V. 

TITLE=Recent advances in electrochemical C—H phosphorylation

JOURNAL=Frontiers in Chemistry

VOLUME=Volume 10 - 2022

YEAR=2022

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2022.1054116

DOI=10.3389/fchem.2022.1054116

ISSN=2296-2646

ABSTRACT=The activation of C–H bond, and its direct one-step functionalization, is one of the key synthetic methodologies that provides direct access to a variety of practically significant compounds. Particular attention is focused on modifications obtained at the last stages of the synthesis of complex molecules, which requires high tolerance to the presence of existing functional groups. Phosphorus is an indispensable element of life, and phosphorus chemistry is now experiencing a renaissance due to new emerging applications in medicinal chemistry, materials chemistry (polymers, flame retardants, organic electronics and photonics), agricultural chemistry (herbicides, insecticides), catalysis (ligands) and other important areas of science and technology. In this regard, the search for new, more selective, low-waste synthetic routes become relevant. In this context, electrosynthesis has proven to be an eco-efficient and convenient approach in many respects, where the reagents are replaced by electrodes, the strength of which is controlled by the applied potential. The electrochemical approach to such processes is being developed rapidly and demonstrates some advantages over traditional classical methods of C-H phosphorylation. The main reasons for success are the exclusion of excess reagents from the reaction system: such as oxidants, reducing agents, and sometimes metal and other additives, which complicate isolation, and increase the amount of waste and reduce the yield due to frequent incompatibility with these functional groups. Ideal conditions include electron as a reactant (regulated by applied potential) and the by-product hydrogen or hydrocarbon. The review summarizes and analyzes the achievements of electrochemical methods for the preparation of various phosphorus derivatives with carbon-phosphorus bonds, and collects data on the redox properties of the most commonly used phosphorus precursors. Electrochemically induced reactions both with and without catalyst metals, where competitive oxidation of precursors leads to either the activation of C-H bond or to the generation of phosphorus-centered radicals (radical cations) or metal high oxidation states will be examined. The review focuses on publications from the past five years.