Research Of C-N And C-C Bond Formation Via C–H Activation

The C–H bond can be found in many organic compounds. C–H bond activationor C–H activation is a reaction that cleaves a carbon–hydrogen bond, which is widelyused in the formation of C-X（X=C,N,P,S）bonds without functionalization of thetargetcarbon. C–N bond forming cross-coupling reactions via C-H activation sharethe following advantages such as atom economy and less operation steps. As C-N andC-C bonds are widely exist in organic compounds, the research of C-N and C-C bondformation via C–H activation bears a lot of research significance.Organic compound containing C-N bond exists commonly in nature, which isessential for composing life. Aromatic amine is very important to our life because it isa main member in bioactive natural products and drug molecules, and it is a vitalmaterial of chemical products. Therefore, efficient, economy and environmental C-Nbond construction is still active in organic compound study.There are many methods to build C-N bond. For example, Ullmann couplingreaction with Cu as a catalyst, Buchwald-Hartwig coupling reaction with Pd as acatalyst and Chan-Lam coupling reaction. These methods are effictive and widelyused in chemical synthesis. But these reactions always need transform Ar-H to Ar-Xby single-step or multistep reaction, it increases synthetic workload and decreasesstep economy. Herein, the construction of aryl C-N bond by means ofdehydrogenation coupling becomes the goal of many organic chemist.Recently, dehydrogenation coupling reaction has made profress. It has beensucceed in build aryl C-N bond by dehydrogenation coupling reation which useorganic oxidant or metal salts. These method have excellent step economy. However,using excessive oxidant like peroxide and metal salts in reaction brings someunavoidable problem, for instance, produce alot of by-product，reduce atom economy,remain a lot of oxidant which makes isolate more difficulty, the high price andcausing environmental pollution. While not only using O2replace organic peroxidesand Metal salts as an oxidant can solve the problem. It is also reported by many otherstudies. Thus, this paper explores using cuprous bromide as catalyst, 2-phenylpyridine species compounds reacted directly with N-acetyl arylamine speciescompounds under air conditions, occurring dehydrogenation coupling reaction so asto form the aryl C-N bond.This paper discusses things as follows:1. with2-phenyl pyridine derivatives and acetanilide derivatives as substrate,CuBr as catalyst, and O2as oxidant, a series of arylamine derivatives has beenefficiently synthesized. Meanwhile this research studies the reaction temperature,catalyst, quantity of catalyst, solvent and its quantity, and proposed a possiblemechanism. With the optimal conditions, nineteen arylamine derivatives wereultimately synthesized with structural elucidations by NMR.2. an efficient method to construct a series of2-(phenoxymethyl) quinoline usingAgNO3as the catalyst, K2S2O8as the oxidant with trifloroacetic acid in the mixturesolvent of water and dichloromethane is reported. This research studies the reactiontemperature, catalyst, oxidant, solvent and time. With the optimal conditions, nineteenarylamine derivatives were ultimately synthesized with structural elucidations byNMR.