Preparation Of Non-precious-metal Photocatalyst And Its Application In SP~3 C-H Activation Reaction

SP³ C-H bond activation reaction is an effective method to construct C-C bond.Through activation and induction of C-H bond,simple starting materials can be directly synthesized into complex organic products without the introduction of activated groups in advance.It embodies atomic economy and environmental friendliness and conforms to the concept of green chemistry today.Tetrahydroisoquinoline and its derivatives can be found in various kinds of plants.Many of the derivatives are biologically active,thus some of which have already been applied in clinical medicine as anti-viral,anti-inflammatory drugs or anti-carcinogen.With further researches on tetrahydroisoquinoline compounds,more derivatives are being synthesized,yet most of which by conventional methods and few with efficient SP³ C-H bond activation according to publications.Light was employed in chemical reactions over a century ago,as the most abundant clean energy in the natural world.In the context of environmentally friendly chemistry,photo-catalysis in red-ox reactions has been developed massively in the past decade.However,currently the photocatalysts used in producing N-aryl-tetrahydroisoquinoline are mostly precious metals.Due to problems such as high prices and high toxicity,precious metal catalyst cannot be the optimal choice in medicine production.Therefore,it is vital to find a non-metal catalyst that is cheap,highly efficient and reactive in mild condition to address the fore-mentioned problems.This paper chose common non-precious-metal halides?Fe,Ni,Co,Cu?and nitrogen heterocyclics?bipyridylium,phenanthroline,etc.?as raw materials and synthesized a variety of non-precious-metal complexes catalysts.By element analysis and NMR,the structure of the catalyst was determined,and the analysis of absorption spectrum was conducted to find the best absorption wavelength of different metal complexes.The spectral data acquisition provided evidence for the selection of wavelength light source for us.Based on this,our preliminary discussion on the non-precious-metal complexes photocatalyst in N-aryl-tetrahydroisoquinoline with nitromethane,benzene methanol oxidation/Aza-Henry,isochromanfull and nitromethane,octanal and dimethyl bromomalonate reactions'application performance concluded that the catalyst in the N-aryl-tetrahydroisoquinoline with nitromethane showed favorable catalytic performance.On the basis of previous work,we further studied the non-precious-metal complexes catalysts in N-aryl-tetrahydroisoquinoline derivatives with nucleophilie of SP³ C-H activation reaction.The study found that the non-precious-metal complex[Fe?bpy?₃]?PF₆?₂ appeared to be the best photocatalyst.Under the conditions of light,the SP³ C-H bond activation between N-aryl-tetrahydroisoquinoline and nucleophile was successfully catalyzed and the yield was up to 81%.This reaction system,with moderate or higher producvitity,is widely applicable and provides a novel way to synthesize N-aryl-tetrahydroisoquinoline.