Study On One Carbon Unit Transfer And Hydrogen Transfer Of Imidazolinium Salt And Imidazolidine

Chapter 1 It is known that tetrahydrofolate (THF) coenzyme is responsible for transfer of one-carbon fragment in the biological synthesis and metabolism. So it is significative to synthesize some model compounds which are analogous with tetrahydrofolate coenzyme in structure by organic synthesis methods and to use them to mimic one carbon unit transfer reaction outside living body. In this paper we found some factors involved in the reactivity of tetrahydrofolate coenzyme models by contrast with imidazolinium salt models before, then synthesized a more active tetrahydrofolate coenzyme model: 1,5-dimethyl-3-(3-nitrobenzenesulfonyl) -imidazolinium iodide and researched detailedly its reactivity. The reseach contents were as follows:(1) Study on reactivity of the imidazolinium salt modelIt was indicated by addition of the model with carbon nucleophiles and nitrogen nucleophiles that our imidazolinium salt model was more electrophilic than those reported before.(2) One-carbon unit transfer reactionIt was detailedly researched that reactions addition product of imidazolinium salt with malononitrile carbon anion with amines as examples of transferring substituted one carbon unit, and a series of enamine derivatives were obtained.The above research results indicated that our imidazolinium salt model could effectively transfer substituted one carbon unit and made transferring one carbon uint varied. Moreover, one carbon uint transfer products, enamine derivatives, could provided important base with synthesis of physiologically active heterocycles compounds, such as tetrahydro-β-carboline, tetrahydroiso-quinoline, indole, dihydroindole- type alkaloid and benzoquinoline derivatives.Chapter 2 In our efforts of developing the imidazolinium salttetrahydrofolate coenzyme models for the one-carbon unit transfer reactions, we first found that N',N3-disubstituted imidazolidine-type compounds could transfer hydrogen as a new type non-metal organic reducing agent and detailedly researched their reductibility. It was indicated that l-actyl-2,3-dimethyl-imidazolidine had stronger reducing ability in our researching imidazolidine-type compounds, because it could high effectively reduce aliphatic aldehydes, aromatic aldehydes, Ts-imines, Ph-imines and 9-fluorenone, and reduce a, (3-unsaturated aldehyde carbonyl groups alternatively, not affecting carbon-carbon double bonds. Based on characteristic and result of this type reactions, we also speculated its reducing mechanism finally.