The Reactions Of 2-acylaryl Functional Isonitriles

Isonitriles are considered as nucleophile and electrophile due to their unique structure which have lone electron pairs and empty orbits simultaneously.Excellent reactivities enable them to participate in constructing various nitrogen-containing compounds.Studies show that 2-acylaryl isonitrile has superior properties to construct quinoline compounds owing to its bi-active reaction sites.However.their further applications have not attracted notable attention.Previous works mainly focused on the silver catalyzed oxidative coupling reaction of 2-acylaryl isonitrile with strong nucleophiles.The purposes of this thesis are to investigate the applications of 2-acylaryl isonitrile in organic synthesis,study its special reactivity,enrich the research of functional isonitrile and construct a series of nitrogen-containing functional organic compounds.This thesis is divided into the following three parts:Part ?:We revealed the reaction of carbon atoms severed as nucleophlic atoms to attack isonitrile with assistance of Cul.According to the activation of the isonitrile by Cul,the rate-determining step triumphantly transformed and constructed more steady products.Hence,the weaker nucleophile carbon atom instead of oxygen atom as nucleophile to attack the isonitrile and a range of significant pharmaceutical intermediate 4-hydroxyquinoline compounds were constructed selectively.Furthermore.these compounds can be transformed into more functional molecular structures with Heck coupling reactionPart ?:A base-catalyzed addition reaction of 2-acylaryl isonitrile with diphenylphosphine was studied.This strategy overcomes the previous disadvantages such as using costly metal catalyst,needing of high reaction temperature and poor atomic economy.The reaction performed at room temperature and showed good compatibility in substrate scope via DBU as the optimized base.In addition,the reaction showed good tolerance for the alkyl isonitriles,which never be used before,Meanwhile,the product could be obtained in gram-scale with good yield.Part ?:A photocatalyed free radical tandem addition reaction of 2-acylaryl isonitrile was studied.The quinolone derivatives could be obtained by using green and environmental LED blue lights as energy sources,easily accessible ethyl bromodifluoroacetate and 2-acylaryl isonitrile as starting materials.