The invention provides a synthetic method of 1,2,5-thiazolinone-1,1-dioxide and 2,3-dihydro-1,2,5-thiadiazole-1,1-dioxide containing quaternary carbon chiral centers. Specifically, according to the method, a monovalent rhodium metal compound together with a chiral phosphorene ligand forms a complex to catalyze an organoboron reagent, so that a 4-substitued-3-carbonyl-1,2,5-thiadiazole substrate and a derivative thereof undergo an asymmetric addition reaction to obtain a corresponding compound containing a quaternary carbon chiral center. The method is good in selectivity, the product can be used for synthesis of multiple crucial chiral compounds, such as alpha, alpha-diaryl amino amide, through further functional group conversion, and has bright industrial production and application prospects.