Visible Light Induced Direct C-H Functionalization Of Aromatic Amines

Aromatic amines are an important molecular skeleton,and are often used in various fields such as agricultural and pharmaceutical products,dyes,pigments,and electronics.The functionalization of C-H bonds in aromatic amines is the most widely used and a key step in drug synthesis.Therefore,people's exploration of the functionalization of C-H bonds of aromatic amines has never stopped,and sp²/sp³ C-H bond activation of aromatic amines is the most common.With the advancement of science and technology,people have developed more and more methods to realize the functionalization of the C-H bond of aromatic amines.However,today,as the environmental protection concept is deeply rooted in people's minds,people have also started to look for the development of environmentally friendly,green and simple methods to achieve Aromatic amines are activated by the C-H bond.As a result,visible light has caught people's eyes.It has the characteristics of wide sources,easy availability,and green cleanliness,and has been favored by researchers.With the hard work of researchers,visible light-catalyzed organic synthesis has also achieved good results.In this paper,two parts of the sp²/sp³ C-H bond activation of aromatic amines are studied:?1?visible light catalyzed para-thiocyanation reaction of aromatic amines,activation of C-H bonds,and construction of C-S bonds;?2?cheap metals The complex photocatalyst catalyzes the activation of sp³ C-H bond at the C1 position of N-aryltetrahydroisoquinoline and the construction of C-C bond.1?A simple and mild method for arylamine thiocyanation was developed.After optimizing the photocatalyst,light source,solvent,and material ratio of the reaction,the best reaction conditions were obtained.Eosin Y was the photocatalyst,the solvent was acetonitrile,and the reaction was performed under the atmosphere of 30 W green LED for24 hours under the oxygen atmosphere.The applicability of the product range was investigated,and a good yield was obtained.A new green method for sp² C-H activation of aromatic amines and construction of C-S bonds at room temperature was achieved.The method is green,environmentally friendly,and low in cost,and does not require transition metal catalysis and strong oxidants.For aromatic amines,whether they are primary,secondary or tertiary amines,the reaction can proceed smoothly,making the reaction widely applicable.2?A series of cheap metal?Fe,Co,Ni,Cu?and other metal complex photocatalysts were designed and synthesized,and applied to the reaction of N-aryltetrahydroisoquinoline with nitromethane.We obtained the optimal conditions for the reaction:the Co?bpy?₃?PF₆?₂complex was a photocatalyst,TBHP was an oxidant,and DMF was a solvent.The reaction was carried out under a 30 W compact fluorescent lamp for 40 hours.Under this condition,We also examined the applicability of the substrate and obtained good yields.Cheap metal complex photocatalysts have a wide range of sources,are simple and easy to prepare,and greatly reduce costs.