| Metal carbene is an important reaction intermediate in organic chemistry and has been widely used in various types of organic reactions.α-Diazocarbonyl compounds are general carbene precursors.In the past few decades,researchers have conducted extensive research and exploration in various types of reactions of diazo compounds.The O-H insertion reaction is one of the most effective methods to construct C-O bonds under transition metal or metal-free catalysis.Phosphorus is one of the most important elements in life and is extensively distributed in nature.Organophosphorus compounds,as important intermediates in organic synthesis,are widely used in medicinal chemistry,agricultural chemistry,modern synthetic chemistry,and materials science.Due to the important research value of organophosphorus compounds,more and more attention has been paid by chemists in recent years,and a series of construction methods of organophosphorus compounds have been developed.However,reports on the use of P(O)-OH compounds to construct organophosphorus compounds through O-H insertion reaction are quite limited.The study work of this thesis has two parts: One is the formation of α-phosphoryloxy carbonyl compounds from borane-catalyzed O-H insertion reactions of α-diazocarbonyl compounds with phosphinic acid;the other one is the stereoselective synthesis of α-phosphonoxycarbonyl compounds.In the first part of the thesis,tris(pentafluorophenyl)borane was used to catalyze the metal-free O-H insertion reaction of α-diazocarbonyl compounds and phosphinic acid.Then the reaction conditions were optimized and screened.Finally,various types of α-phosphoryloxy carbonyl derivatives can be obtained in a yield of up to 99% by one step under green reaction conditions.A highly efficient base-,metal-,and oxidant-free catalytic O-H insertion of diazonium compounds and phosphinic acids have been developed.The protocol features advantages of operational simplicity,high atomic economy,practical,easily scaled-up,and environmentally friendly.In the second part of the thesis,a preliminary exploration was made on the asymmetric catalytic synthesis of α-phosphonooxycarbonyl compounds derivatives.By screening different metal catalysts,chiral organic small molecule catalysts,the temperature,and solvent,an asymmetric synthesis method of α-phosphonooxycarbonyl compounds derivatives has been preliminarily determined.The maximum enantiomer excess(ee value)was 37%. |
