The Study Of The Stereoslective Reaction And Synthesis Of Chiral Dihydrocarbyl Phosphine Oxide

Organic phosphorus chemistry, which is closely related to human life, has beenapplied in a wide range of fields, such as medicine, agriculture and biological engineering.This study focuses on the synthesis and reaction stereoselective mechanisms of (RP)-α-Hydroxyl phosphine oxides containing two P, C-stereogenic centers;1,3-Bisphosphino-1-alkanols containing four P, C-stereogenic centers; Sulfanylphosphine oxides.Secondary (RP)-phosphine oxide that has up to drP>99:1were prepared fromreactions of the Grignar of L-(-)-Menthol to dichlorophenylphosphine and Hydrolysis.(RP,SC)-α-Hydroxyl phosphine oxides have been obtained by the stereoselectiveadditions of (RP)-phosphine oxide, which has up to drP>99:1, to cinnamaldehydederivatives, aromatic aldehydes or aliphatic aldehydes that have C=O bonds to be added.The reactions catalyzed by bases (potassium hydroxide or calcium hydroxide) at roomtemperature have been up to drP,drC>99:1and99%yields. The diastereoselectivity wasinduced by reversible equilibrium and different stabilities between two stereomers ofadduct, which was caused by the spatial interaction between menthoxyl to alkyl groups ofaldehydes. The two isomers of dihydroisobenzofuran phosphine oxide compounds havebeen obtained by different post-processing methods of (RP)-phosphine oxide todialdehydes, such as o-Phthaldialdehyde.P,C-Stereogenic1,3-bisphosphino-1-alkanols that have up to four or five stereogeniccenters were prepared from one step of reactions of secondary (RP)-phosphine oxide tovinyl aldehydes in up to drP,drC>99:1and excellent yields. The reaction was catalyzed byKOH, carried out at room temperature, and supposed to proceed via1.2-addition of P-Hspecies to aldehydes, stereoselective intermolecular shift of phosphorus via asix-membered cyclic intermediate, and the addition of second phosphorus to the resulted1.4-adducts.Sulfanyl phosphine oxides that have up to drP>99:1were prepared from reactionswith secondary (RP)-phosphine oxide and further reacted with lithium phenylacetylene to obtain sulfanyl styryl phosphine oxides.