The Synthesis Of Chiral Phosphines And Nitriles With Chiral Tridentate Pincer Nickel Complexes

Organic phosphine and nitrile compounds have unique biological,physical and chemical properties,and many drug molecules containing phosphine or cyano groups have been developed and applied in many fields such as anti-tumor,antibacterial,antihypertensive,and enzyme inhibition.Since the stereomorphism of the molecule has a great influence on its activity,it is important to develop efficient and highly selective chiral phosphine and nitrile compound construction methods.On the other hand,chiral tridentate pincer metal complexes have the characteristics of good stability and easy modification,and have shown great application in asymmetric catalytic reactions.This paper focuses on chiral tridentate pincer nickel complexes to study its application in asymmetric catalytic synthesis of chiral phosphine and nitrile compounds.The specific work carried out is as follows:1.Six examples of chiral tridentate pincer nickel complexes were obtained by multistep reaction synthesis.Using diphenylphosphine and electron-deficient enones as substrates,chiral tridentate pincer nickel as catalyst,potassium acetate as base,and acetonitrile as solvent,and chiral phosphine compounds were successfully synthesized with a yield of up to 92%and 98%ee2.Using phenylphosphine and electron-deficient enones as substrates,chiral tridentate pincer nickel nickel complex as catalyst,and dichloromethane as a solvent,the tandem cyclization reaction was carried out at a reaction temperature of-40℃,and the chiral phosphine heterocyclic compound was synthesized at a yield of up to 79%and 98%ee.3.Using acetonitrile and ketones as substrates and chiral tridentate pincer nickel complexes as catalysts,chiral nitrile compounds were synthesized at room temperature.However,the enantioselectivity was greatly affected by the water in the reaction system.In addition,the deuterated nitrile compounds were synthesized with the yield of 34-68%via addition reaction of deuterated acetonitrile and ketone compounds.