Design,Synthesis And Configuration Control Of Carbon,Phosphorus And Axis-chiral Tertiary Phosphines

Chiral biphenylphosphine ligands play an important role in asymmetric catalysis,organic synthesis and bioengineering.Biphenylphosphine ligands containing carbon,phosphine and axially complex chiral centers can improve the induction effect in asymmetric catalysis.The paper focuses on four parts: The synthesis of stereospecific chiral biphenyl monophosphine compounds from 6-Chloro-6H-dibenzo[c,e][1,2]oxaphos-phinine(CDOP)without chirality;The synthesis of chiral biphenyl secondary and tertiary phosphines and bisphosphonates;The study of axis Chirality Control;The intramolecular cyclization and coupling of chiral biphenyl tertiary phosphine compounds.Firstly,the chiral centers of phosphorus atoms were induced by the reaction of CDOP with menthyl Grignard reagent.After a series of separation and transformation,the optically pure 3,4 and 5 were obtained.Secondly,de-protection of 3 reacts with Grignard reagents,and further protects with borane to obtain chiral tertiary phosphine borane complexes 7 with reversed phosphine configurations.A series of chiral secondary and tertiary phosphines 9 ? 10 or diphosphosphine 11?12?13?14 compounds were synthesized by selective O-alkylation or P-alkylation of 5 under alkaline or phase transfer conditions.Then,biphenylphosphine derivatives with high optical purity and high yields were synthesized by cyclization or coordination with metal ions.The flexible axially chiral of chiral biphenylphosphine compounds were fixed.Finally,we used chiral tertiary phosphines 10 to react with LDA to achieve intramolecular cyclization by intramolecular nucleophilic substitution catalyzed by cuprous iodide.We fixed the axis of biphenyl and introduced the chirality of carbon.Finally,a complex chiral compound 21 with carbon,phosphorus and axis chirality greater than 99:1 were obtained,and their alpha site were further modified.