Study On The Application Of ?-hydroxy Phosphonates In The Synthesis Of Phosphorus Compounds

The ?-hydroxyl phosphorus derivatives were widely applied in organic chemistry,organic biochemistry,and pharmacology.In this master's thesis,?-hydroxyl phosphorus derivatives were employed as starting materials for the following researches.At first,a series of functional phosphorus compounds were synthesized.The functional P-derivatives attracted extensive attention in recent years because of their widely pharmacological and biological applications.We applied the?-hydroxyphosphonate derivatives to the synthesis of functional P-containing compounds.?-Chlorinated allyl phosphonates were obtained via chlorination of ?-hydroxy phosphorus compounds with thionyl chloride.Catalyzed by palladium acetate,the ?-chlorinated allyl phosphonates were rearranged and coupled with amine,affording ?-imino or enamino P-compound as an intermediate.?-Carbonyl phosphonates were obtained via hydrolysis of the intermediate,which were reduced by sodium borohydride to form ?-hydroxy phosphonates.Imine or ?-enamines were reduced by sodium borohydride to form a?-amino phosphonates.In addition,the Stork reaction of ?-enamino phosphorus compounds afforded ?-alkyl ?-carbonyl phosphonates.Secondly,the synthesis of P-heterocycles compounds exhibited excellent activities as ligands in transition metal catalysis.We employed ?-hydroxy phosphonite derivatives for the synthesis of phosphindole or isophosphindole compounds.The addition of benzyl or naphthyl substituted H-P species to aldehyde afforded ?-hydroxy phosphorus derivatives,which were dehydrated to afford the phosphindole and isophosphindole compounds respectively.Various dehydrating agents were examined,and 80% sulfuric acid/ polyphosphoric acid was found to form isophosphindole compounds in higher yield.Under the optimal condition,sixteen kinds of isophosphindole compounds that contained various substituents were synthesized.Because of the carbon and phosphorus two chiral centers in the products,two diastereomers were obtained in the ratio near to 1:1.After recrystallization,one of them was isolated.Under the condition of PPA/100 oC,ten kinds of [cd] phosphindole compounds were synthesizedvia naphthyl substituted ?-hydroxy phosphonites.