Iron Complexes Synthesis And Their Applications In C-N Formation Reaction

Nitrogen-containing compounds are widespread in pharmaceutical molecules,natural products and functional materials.Developing simlpe and efficient method to constructe C-N bonds has practical values.One of the widely used methods to form C-N bond is the cross-coupling reaction between halide and amine,which is inefficient operation and low atom economy.During the past decade,the strategy of directly constructing C-N bonds through transition metals catalyzed C-H activation has been widely used.Compared with commonly used noble metals such as ruthenium,rhodium,iridium and platinum,iron is cheaper,more available,less toxic and more biocompatible,so the use of iron to catalyze C-N bonds formation reaction has become a subject of major concern in this field.This thesis aims at using Fe(Ⅱ)complex as catalyst for an efficient and highly enantioselective formation of C-N bonds.The research includes the followings:In the first part of this thesis,cheap and readily available iron(Ⅱ)phthalocyanine[tBu4PcFe]efficiently catalyzed intramolecular C(sp3)-H bond amination of various alkyl azides.Series of pyrrolidine and imidazolidine derivatives were obtained with yields up to 97%.This catalytic system has a practical application value due to its ease to operate,wide tolerance range of substrates,and ability to efficiently synthesize multiple important precursors of alkaloids,pharmaceutical molecules and derivatives of natural products.Aziridine compounds are important intermediates in organic synthesis.It is meaningful to develop a transition metal catalyzed aziridination reaction of olefins,especially asymmetric aziridination.In the second part of this thesis,a series of chiral polypyridine iron(Ⅱ)complexes synthesized and characterized.These chiral iron(Ⅱ)complexes were used to catalyze asymmetric aziridination of olefins with imidoiodinane(PhINTs)as nitrogen source.The corresponding products were obtained with yields of 40-60%and ee up to 30%.