Study Of Copper-Catnlyzed Intermolccular Diamination Of Styrenes

Nitrogenous organic compounds exist widely in medicine, agriculture, biology and othermolecules, which have important pharmaceutical and biological activity, therefore,developing new method to formation C-N bond is a long-term objective for organic synthesisworkers. Since2001, three times Nobel Prize in chemistry research work involved the veryimportant conversion reaction of olefins. The difunctional reaction of olefins has received thewidespread attention, because it can almost introduce arbitrary two functional groups at thesame time. Difunctionalization of olefins usually use expensive catalysts,such as palladium,nickel, gold, in which the byproducts are difficult to deal with and it will cause environmentalpollution. So the inexpensive, low toxicity copper catalyst has an attractive advantage.In recent years, various aminative difunctionalizations of olefins, such as diamination,aminooxygenation, aminohalogenation and carboamination have been achieved. According todifferent olefins, different nitrogen sources can be chosen. Most of the aminativedifunctionalization need one step of intramolecular amination. Therefore, it is an extremelychallenging and very valuable work to develop a general diamination starting from the samenitrogen source. Meerwein aromatization reaction based on aryl radical is a generalbifunctional methed of olefin. At present, there is no corresponding aminativedifunctionalization reaction.This paper developed a new way to construction C-N bond. By employing commerciallyavailable nitriles and NFSI as nitrogen sources, the first copper-catalyzed strictlyintermolecular diamination was developed (no intramolecular amination involved for bothamination steps), in which, NFSI was efficiently utilized as a radical nitrogen source. Thecombination of radical and nucleophilic nitrogen sources result in the high regioselectivity ofthe diamiantion. Low loading of copper catalyst, mild conditions and compatible with a widevariety of functional groups made this method very attractive. What`s more, a preliminaryreaction mechanism has been explored. This work has laid a solid foundation for thedevelopment of aminative difunctionalization of olefins.