Synthesis Of Biphenol-based Thiomenthylphosphine Oxide Compounds And Their Application In Stereoselective Carbon-phosphorus Bond Formation

Chiral phosphine ligands have important applications in asymmetric catalysis,organic synthesis,and biological engineering.Among them,chiral phosphorothioate and related compounds are widely used as agricultural pesticides due to their important biological activities.This thesis is mainly divided into two parts:a series of stereospecific chiral thiophosphoric acid derivatives are prepared from achiral CDOP,including the preparation of chiral thiophosphoric acid and the preparation of chiral thiophosphonate compounds;Based on the regional/stereoselective cleavage of phosphorus-sulfur bonds by lithium naphthalene reagents and a series of chiral trihydrocarbylphosphine oxide compounds with high selectivity and high yield are synthesized by this method.First,the chiral center of phosphorus atoms is induced by the reaction of non-chiral CDOP with mint-based Grignard reagent,and the stable mixed phosphorus atom chiral compound is synthesized by reacting with sulfur under 4/4',4/4'alkaline conditions.After hydrolysis,it recrystallizes the optically pure chiral thiophosphoric acid SP-5,and the mother liquor 5/5'recrystallizes out a single phosphorus atom chiral compound SP-3'after a series of separation operations.It is hydrolyzed after reacting with Lawson reagent.An optically pure chiral thiophosphoric acid RP-5'was obtained with the configuration maintained.Secondly,Sp-5 was subjected to oxyalkylation or thioalkylation under basic and heat conditions to prepare a series of chiral thiophosphonates SP-6 with the phosphine configuration maintained.and achieved a considerable yield.Then,P-S bond and S-C bond of the chiral phosphorothioate SP-6 were carried out by the format reagent or lithium naphthalene reagent.at 50 ~oC,the excess naphthalene of lithium naphthalene reagent was used to break the bonds,thereby realizing the SP-6 region/stereoselective bond breaking.Finally,we used the above-mentioned optimal bond-breaking method to break the P-S bond of Sp-6b,and a series of chiral trihydrocarbylphosphine oxide compounds with a phosphine configuration were prepared by alkylation reaction yield,and Selectivity greater than 99:1.