Formation Of C-N And C-B Bonds Catalyzed By Transition Metals

Functionalized aromatic amine skeleton compounds and organoboron compounds are very important organic intermediate and widely presented in modern organic synthesis.It has important application prospects in the fields of chemistry,pharmaceuticals,functional molecules,environmental monitoring,disease diagnosis and industrial materials.In particular,compounds containing an amino-bis(hetero)arylamine skeleton are often used as intermediates for the synthesis of pharmaceuticals and organic materials,such as the currently best-selling drugs Gleevec(imatinib)and prasole(olanzapine).Boric acid derivatives are easy to purify and have good structural stability.They can be used in transition metal catalyzed cross-coupling reactions between organometallic reagents and electrophiles.Therefore,the synthesis of their synthesis methods is a very valuable research direction.Arylboronic acid(borate)are indispensable important raw material in organic synthesis,especially in the transition metal catalyzed cross-coupling reaction,carbon heteroatoms can be formed,the reaction process is simple,the conditions are mild,the functional group compatibility is high,and the toxicity is low.Therefore,such compounds are widely used in the synthesis of pharmaceuticals,pesticides,liquid crystals and organic photoelectric materials.Combining with the current research progress of transition metal catalysis,this paper firstly summarizes the development of C-N bond and C-B bond in recent years,and focuses on the Miyaura coupling reaction and Buchwald-Hartwig coupling reaction as well as the effect of different types of ligands on the reaction.On the basis of previous studies,the main research results of this paper are as follows:In the first chapter,through a lot of literature researches,we found that the synthesis of aminodiarylamine in order to solve the problem on a single component,which two components can also be achieved by one-pot method in this reaction.The realization not only bypasses the intermediate separation and purification steps but also improves the synthesis efficiency and economy.However,there are some certain challenges in this reaction,which is the compatibility of the two(multiple)components.In view of these factors,we found that the dialkyldiarylphosphine ligand has a mild reaction condition and a good functional phase fusion compared to the conventional method.Therefore,we choose to use the Buchwald-Hartwig coupling to achieve the amination process.The non-toxic and commercial boron-based reagent Bpin-Bpin have been reported to achieve metal-free nitro reduction,which is undoubtedly our first choice to explore amination/reduction of one-pot synthesis of amino-bis(hetero)arylamine.In the second chapter,combined with Buchwald-Hartwig cross-coupling,the chemoselectivity in the coupling reaction is changed by changing the catalyst(palladium/copper)to realize the synthesis of various oligoanilines.In the process of iterative proliferation,we explored the effect of electron with drawing groups and electron donating groups on the composition and its properties.And its electrochemical performance was tested by CV and DPV.In the third chapter,through the synthesis of asymmetric boron reagent Bpin-Bdan,we explored the selective transfer of boron-based B(dan)under transition metal catalysis,effectively completing the synthesis of alkyl boronate and(poly)boron compounds under the catalyst of palladium/copper and the optical physical properties of(poly)boron compounds were tested.In summary,this paper mainly explores the construction of C-N bonds in amino-di(hetero)arylamines and aniline oligomers by palladium/copper catalysis,and synthesizes C-B in alkyl boronate and aryl(poly)boron compounds.And their performance in photoelectrochemistry was tested.