Novel Reactions Of Transition-metal Carbene For C-P Bond Formation

C-P bonds construction is present in a wide variety of materials such as proteins,nucleotides,neurotoxins and other phosphine ligands in metal catalysis.The traditional methods for carbon-phosphorus bonds formation mostly based on mutual conversion between functional groups with the low selectivity and low atom economy,which can not meet the increasing needs of complex organic phosphine compounds with variety of functional groups in medicine,chemical and agricultural production.Exploration of efficient methods for carbon-phosphorus bond formation has important theoretical and practical significance in organic synthesis.Transition-metal-catalyzed heteroatom-hydrogen bond(X-H)insertions via a metal carbene intermediate represent one of the most efficient approaches to form C-X bonds.Herein,transition-metal-catalyzed P-H insertion reaction of azavinyl carbenes and P(O)-H compounds has be studied for C-P bond formation.In addition,we have explored the asymmetric catalytic of P-H insertion reaction of novel azavinyl carbine,which provides a new simple,efficient and green approach to construct a series of multi-functional,complex compounds that contain C-P bond and has very important significance for drug screening and pharmaceutical technology.Research work of this thesis has two parts:First,study of P-H insertion reaction of new metal carbene,second,exploration of the asymmetric catalysis P-H insertion reaction.In the first part of the thesis,we screened the metal catalysts,and found that not only RhⅡ but also RhⅠ,and Ni can catalyze the reaction and were able to synthesis the desired product in a moderate yield.After select the reaction conditions,the final yield can reach 60%-70%.After a lot of exploration,we have achieved the new metal carbene participation P-H insertion reaction,which is a new way to build C-P bond.In the second part of the thesis,we tried to research the asymmetric catalysis P-H in new metal carbene insertion reaction,Ultimately,we identified the analysis conditions of liquid chromatography:Daicel chiral column:AD-H;liquid:V(Hexane:isopropanol:methanol)=5:1:1;UV=254nm;Velocity of flow:0.8mL/min.Use the 1,2,3-triazole and hydrogen phosphonate compounds as starting materials,we have synthesized the compounds of enamine that containing phosphine.Through a single metal catalysis,metal and small molecule synergy catalytic,we made an initial progress in asymmetric catalysis.