Synthesis Of Four-coordinate Boron-nitrogen Compounds And Their Application In Photo/Metal Synergistic Catalysis

Metal photocatalysis is different from the previous photocatalytic mode.Metal photocatalysis can activate organic molecules with high redox potential.However,most of the reaction systems rely on the use of noble metal complexes such as ruthenium and iridium as photocatalysts,and the development and research of organic photocatalysts with low cost,wide substrate adaptability and good catalytic performance are not deep enough.In this thesis,based on the synthesis of N,N’-chelated tetracoordinate organic boron compounds,nickel/tetracoordinate boron nitride catalyzed metal photoredox platform for the construction of carbon-heteroatom bonds,copper/tetracoordinate boron nitride catalyzed olefin alkyne hydroboration reaction related research.（1）N,N’-chelated tetracoordinate organic boron compounds have been widely used in various fields of science and technology.Tetracoordinate organoboron compounds（BAr₂（N,N））have unique luminescent properties and can be regulated by various substituents in the N,N’-chelating framework.In general,the development of organic BAr₂ complexes mainly depends on the design and synthesis of bidentate organic ligands.Here,aryl trifluoroborate was developed as BAr₂ source,simple aromatic amines as ligands to introduce different aryl sequences with different functional groups,and a simple and effective method for the synthesis of tetracoordinate borane was developed.In addition,the fluorescence test found that the compound has certain optical activity and can be applied to a series of visible light photocatalytic oxidation reactions.（2）As a cheap substitute for noble metals such as ruthenium and iridium,nickel was initially used in traditional cross-coupling reactions,but because it can carry out single electron transfer（SET）,energy transfer（ET）or free radical capture reaction,it has played a more prominent role in the field of metal photocatalysis.In fact,the combination of nickel and photoredox catalysis has been used to form different carbon-carbon and carbon-hetero-atom bonds that are often difficult to achieve by previous synthetic methods.In this thesis,organoboron photocatalyst aminoquinoline diarylboron（AQDAB）and nickel catalyst were used in the cross coupling reaction of C（sp²）-P and C（sp²）-S catalyzed by metalloporphyrin.This strategy effectively couples aryl halides with diarylphosphine oxide and mercaptan at room temperature and in air atmosphere,so as to provide corresponding triarylphosphine oxide and thioether with generally moderate to good yields.（3）Organic boron compounds are essential components in organic synthesis.These important compounds are used as precursors for many important organic synthesis reactions.Due to the cheapness and availability of copper,copper-catalyzed borohydride reaction is still the most concerned reaction.The organoboron photocatalyst aminoquinoline diarylboron（AQDAB）and copper catalyst are used for the borohydride reaction of alkenes and alkynes.Under mild conditions,hydroboration products with excellent non-enantioselectivity and high functional group tolerance were isolated at high yield.