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Reactions involving organophosphorus radicals have a long history,and are useful reactive species in organic synthetic chemistry.1 The last few years have witnessed the importance of P-centered radicals in the construction of carbon–phosphorus bonds.2 Moreover,manganese(Ⅲ)reagent,an important oxidant for the initiation of free-radical,is usually used in P radical reactions under mild conditions and good functional group tolerance.1c Our continued interest in P-C formation recently prompted us to develop new methods involving P-centered radicals initiating by manganese(Ⅲ)acetate to construct P-C bond.As shown in Scheme 1,we have successfully developed a highly efficient and general method for the preparation of β-hydroxyphosphonates through Mn(OAc)3-mediated radical oxidative phosphination of alkenes under relatively mild reaction conditions.We also developed a simple,highly efficient,and general method for the preparation of dialkyl 6-phenanthridinephosphonates through Mn(OAc)3-mediated radical phosphonation of 2-isocyanobiaryls which allows the direct formation of P-C bond and the construction of a phenanthridine ring in one reaction(Scheme 2).