Chiral Menthyl Phenyl Phosphine Oxide Was Used To Construct Asymmetric Carbon-phosphorus Bonds

Organic phosphorus chemistry is closely related to human life, and has a very important application in medicine, biological engineering, agriculture, especially in relating research of chiral phosphorus compounds which has attracted more and more attention. In this thesis, we focused on the addition of(RP)- alpha-Hydroxyl phosphine oxides with imide, its non-racemic alkylation, and the study of the different phosphorus compounds reduction methods.In this thesis, we expounded the background and significance of the synthesis of asymmetric carbon-phosphorus bond from chiral menthylphenylphosphine oxide Alpha-aminophosphonate and the racemic phosphorus-alkyl compounds has been prepared in good yields and stereoselectivity from(RP)-menthyl phenyl phosphine oxide. And the different phosphorus compounds reduction methods were also studied.We studied the synthesis of a series of aminophosphonate compounds using different substituted imine Schiff base with the optical pure(RP)-menthyl phenyl phosphine oxide. Through the exploration of the reaction conditions, we found that this reaction could give excellent yields and good enantioselectivity at 80℃ for 12 hours, without any solvents and catalytic additives. Through the X-ray diffraction single crystal structural analysis, we found that the configuration of phosphorus atoms were retained, and a new chiral center at the imine carbon attached to the phosphorus atoms was formed. We also found the configuration of imine impacted on the stereoselectivity of product. Therefore, we speculated that addition reactions of(RP)-menthyl phenyl phosphine and chiral imines through double asymmetric induction.We also studied the alkylation of optical pure(RP)-menthyl phenyl phosphine oxide with different functional groups, used DMF as a solvent, and calcium hydroxide and potassium iodide as the catalysts at room temperature or 70℃. The reaction obtained products with excellent yields and good enantioselectivity. We explored the racemation of optical pure(RP)-menthyl phenl phosphine oxide under different alkali and solvent, and no occurrence of racemation was found. Then single phosphorus and phosphate complexes were obtained by reacted with different halides.We also studied to get chiral phosphine ligands by the reduction of chiral triphenylphosphine oxides, through cerium chloride, sodium borohydride e.g. The results showed that we could get the borane compounds containing chiral phosphorus atom dramatically.