Study On Photocatalytic Amination Of Olefin By Intermolecular Addition

Nitrogen-containing heterocycles are an important part of amine compounds.They are the skeleton structure of natural product molecules and synthetic macromolecules,as well as important synthetic intermediates,raw materials or fine chemicals.In this paper,the addition amination reaction of phthalimide and alkene with porphyrin iron(?)or phthalocyanine iron(?)as photosensitizers under light conditions is studied.The results showed that the reaction selectively proceeded with the C-N addition reaction and produced a series of compounds containing the aza-seven-membered ring benzazepine structure.This study explored the best reaction conditions,30 ?,nitrogen protection,triethylamine provides basic conditions,the yield of C-N addition amination product is 99.0%.On this basis,the scope of the substrate was investigated,and the results showed that the reaction is suitable for a variety of olefins,and the yield of aliphatic olefins is higher than that of aromatic olefins.In addition,the influence of the light source was further studied.Using a simple low-power insect trap lamp(6 W,365 nm)as the light source for the reaction,HPLC showed that a high yield of 95.0%was obtained.This synthetic method provides a green and effective way for compounds containing aza seven-membered ring benzazepine structure.In order to obtain stereoselective addition amination products,it is studied to use photosensitive and optically active benzothiazole sulfoxide as the chiral template for the addition amination reaction to participate in the addition amination reaction.Peroxides derived from cyclohexanone(peroxides derived from cyclohexanone)is an alkyl peroxide,which is easily available and more reactive than TBHP and does not show acidity,making it easier for industrial applications.Using hydrogen peroxide and cyclohexanone to prepare cyclohexanone peroxide can oxidize benzothiazolyl sulfide containing multiple functional groups.The study found that the reaction can be carried out under the condition of no catalyst,45 ? and methanol as solvent.The yield of sulfoxide is higher than 90%.There is no or almost no double bond on the proximal end of the benzothiazolyl moiety,N and S atoms.Nothing happens.Phenyl sulfide is also used as a substrate to expand the substrate range.The results showed that phenyl sulfide was highly selectively oxidized to sulfoxide within 1 hour.This part of the research established a mild,environmentally friendly,catalyst-free aryl sulfide vulcanization method.However,in the stereoselectivity experiment,the chiral benzothiazole sulfoxide used as a template failed to obtain an obvious stereoselective addition amination product.