Study Of The Selective Phosphorylation Of Carbon-Carbon Double/Triple Bonds

Organophosphorus compounds have a wide range of applications in biology,chemistry and materials science.Therefore,the development of efficient and environmentally friendly new methods for constructing C-P bonds is of great significance.Atherton-Todd reaction and Michaelis-Arbuzov reaction are traditional methods for preparing organophosphate compounds,but the above reactions usually require the use of water-oxygen-sensitive phosphorylation reagents,and have defects such as low selectivity,harsh conditions and low functional group tolerance,thus limiting the use of the above methods.With the development of modern organophosphorus chemistry,chemical selectivity and atom economy have become the focus of attention of chemists.In this thesis,a series of studies have been carried out on the selective phosphorylation reactions involving carbon-carbon double bonds/triple bonds.The details are as follows:（1）A simple and efficient method for the regioselective iodophosphoryloxylation of alkenes with P-OH bonds has been established by using NIS（N-iodosuccinimide）as the iodination reagent.The alkenes can form an intermediate of iodonium ion under the attack of NIS in the THF,and the corresponding iodophosphorylation reaction can be realized through the intermediate under the attack of P-OH bonds.The protocol is compatible with various olefins and compounds containing P-OH bonds under transition-metal-free and mild conditions.A variety of functionalizedβ-iodo-1-ethyl phosphinic/phosphoric acid esters are obtained in good to excellent yields.（2）A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides（p-QMs）with P（III）-nucleophiles has been established via Michaelis-Arbuzov-type reaction.A broad range of P（III）-nucleophiles and para-quinone methides are well tolerated under the mild conditions,giving the expected diarylmethyl-substituted organophosphorus compounds.Moreover,a series of corresponding enantiomers（Rp+Rc/Sp+Sc）and（Sp+Rc/Rp+Sc）-products can be synthetized by employing dialkyl arylphosphonite（Ar P（OR）₂）as substrates.（3）A general protocol for the regioselective phosphorylation of alkenes has been established by using Cu-2D-MOFs as heterogeneous catalyst.The catalyst can be prepared by mixing and heating copper nitrate,tetrafluoroterephthalic acid and 4,4’-bipyridine for 24 h.As a heterogeneous catalyst,this material can catalyze the selective addition reaction of aromatic compounds containing P-H bonds and alkynes under the condition of inorganic alkali sodium bicarbonate to realize the synthesis of alkenyl phosphonate compounds.Under the condition of organic base triethylamine and oxygen,the coupling reaction of alkoxy compounds containing P-H bonds with alkynes could be catalyzed to realize the synthesis of alkyne phosphonate compounds.At the same time,the heterogeneous catalyst can be recovered and reused.