This manuscript summarizes the results of studies on the application of the reaction of dialkyl (aryl) phosphoramidate anions with carbonyl electrophiles for stereospecific synthesis of P-chiral biophosphates (Stec reaction). Following the results obtained with organic phosphoramidates which delineated the scope of the reaction and its stereochemical course, the application of the title reaction is presented for the preparation of diastereomerically pure P-chiral cyclic nucleotide analogues (phosphorothioates, phosphoroselenoates, phosphoroselenothioates, isotopomeric ¹⁸O-phosphates), and P-chiral nucleoside monophosphate analogues, as well as dinucleoside phosphate analogues (phosphorothioates, methanephosphonates).