ABSTRACT
Organophosphorus compounds have all along attracted considerable attention as they have broad utilities such as reagents for chemical reactions, ligands for transition metal catalysts, flame retardants, biologically active molecules and building blocks in synthetic chemistry. Compared with metal-catalyzed coupling synthesis, transformations via P-center radicals processes are powerful methods for the synthesis of organophosphorus compounds, as they provide unique routes leading to target molecules in least and concise steps. Generally, homolytic cleavage of P-H bonds serves as a major approach for the generation of P-centered radicals. And the reaction varieties between P-centered radicals and unsaturated compounds including addition reactions, addition/dehydrogenation reactions and difunctionalizations.
This review will focus on the difunctionalization reactions between unsaturated compounds and P-centered radicals origin from P-H compounds published in the period from 2010 to October 2016, by highlighting the reactions' specificity and, where possible, the relevant mechanistic rationale.