OPTICALLY ACTIVE SILYL ESTERS OF PHOSPHOROUS. II. STEREOCHEMISTRY OF REACTIONS WITH NUCLEOPHILES

Article abstract of DOI:10.1016/S0040-4020(01)89077-3

We report the stereochemistry of reactions of various nucleophiles with optically active silyl esters of phosphorus of general formula: tBuPhP(X)OSiMePhNp X= -(1), Oxygen (2), Sulfur (3), Selenium (4).The list of nucleophiles includes O,S,N,C nucleophiles as well as halides.The nucleophilic attack is essentially directed towards silicon.The phosphinuos and phosphonic acid esters react with predominant retention of configuration at silicon atom, whereas the thiono and seleno crossover is explained in terms of possible interaction of the electrophilic part of the nucleophile with the oxyphosphoryl group or tricoordinate phosphorous.