Application Of [Ph₃C][B（C₆F₅）₄] In Catalytic Hydroamination And Alkylation Reactions Of Amines And Alkenes

Non-metal catalyst [Ph3C][B(C6F5)4] has been developed for hydroamination reaction of vinylpyridines,and hydroarylation of aromatic amines.This method provides a simple and efficient method to prepare amine derivatives,and works in complementary with transition metal catalysts.Possible catalytic mechanisms of the above reactions were also studied.The main results are listed below:1.Hydroamination reaction of vinylpyridines catalyzed by [Ph3C][B(C6F5)4]The readily available borate [Ph3C][B(C6F5)4](TB)showed good catalytic activity for hydroamination of vinylpyridines with aliphatic and aromatic amines.The reaction of2-vinylpyridine and 6-methyl-1,2,3,4-tetrahydroquinoline was studied as a model reaction.Reaction conditions,including reaction temperature,solvent,catalyst loading,substrate ratio and borate reagent,were optimized.The best result was afforded at 80 o C within 12 h in the presence of 10 mol% catalyst loading.This simple protocol was applied for a broad range of aliphatic and aromatic amines,which generally gave 100% anti-Markovnikov products in 28-99% yields.The steric property of the amine had an influence on the efficiency of the reaction.For primary amines,dipyridylethylation products were observed under the same reaction conditions.2.Hydroarylation reaction of aromatic amines catalyzed by [Ph3C][B(C6F5)4][Ph3C][B(C6F5)4] has been developed to catalyze hydroarylation reaction of alkenes with aromatic amines.The reaction of styrene and 1,2,3,4-tetrahydroquinoline was chosen as a model reaction.Optimization of reaction conditions included changing reaction temperatures,solvents,catalyst loadings,substrate ratios and borate reagents.Under optimized conditions,the scope of the substrates was studied.This catalytic system was applicable to aromatic primary,secondary,and tertiary amines,highly regio-and chemo-selective,and provided 100% Markovnikov ortho-products in 32-98% yields.In addition,a kinetic study was conducted to further investigate the reaction,and a plausible mechanism was proposed.