Design,Synthesis And Coversions Of Tertiary Phosphine Derivatives Containing Multi-Chiral Centers

Chiral tertiary phosphine ligands play an important role in asymmetric catalysis,organic synthesis,biological engineering,etc.,and are important fields in asymmetric organic reactions.This thesis is mainly divided into four parts:the addition reaction of R_Pand S_P-menthyl deriving secondary phosphine oxides to activated alkynes;the alkylation reaction of R_Pand S_P-menthyl deriving secondary phosphine oxides;intramolecular cyclization of chiral biaryl tertiary phosphine compounds;?-position modification reaction of phenanthrene tertiary phosphine derivatives.First of all,the additions of R_P and S_P-menthyl deriving secondary phosphine oxides to alkynyl esters 2 stereo selectively afforded bis-phosphinolylated derivatives having up to four C-and P-stereogenic centers.The stereochemistry was controlled by kinetic and thermodynamic processes at lower and higher temperature,respectively.At 100~oC,the bis-adducts were obtained in up to 99%yield and>99:1 dr.Secondly,R_P and S_P-menthyl deriving secondary phosphine oxides 1 reacted with different dihalogenated hydrocarbonsunder phase transfer condition to complete alkylation synthesized a series of tertiary phosphorus compounds,which had various C-and P-skeletons.Third,based on the research work of our research group,the diastereomeric mixture of secondary phosphine oxide was treated with oxalyl chloride,and then reacted with Grignard reagent,under the protection of borane,a series of biphenyl tertiary phosphine borane complex 12 were obtained with high to 90%yield and 99:1 dr.The compound 12was then reacted with n-butyllithium to achieve intramolecular cyclization by intramolecular nucleophilic substitution catalyzed by cuprous iodide.The biphenyl axis was fixed while carbon was introduced.Finally,tertiary phosphine borane complex 13 with a composite chiral center of carbon,phosphorus,and axial chirality greater than 99:1.Finally,the?-position of the phenanthrene phosphine tertiary phosphine derivative is further modified by coupling reaction,reaction with diiodomethane or addition with aldehyde.