Chlorination In The Difunctionalization Of Alkenes

Organic azides have shown wide applications in material science,chemical biology and drug discovery due to their potential application as versatile intermediates in organic synthesis.Chlorides are also very useful intermediates.Therefore,the development of new methods for highly efficient and reliable incorporation of an azide group and chloride group into organic molecules has attracted much attention.The difunctionalization of alkenes is an effective method for simultaneous forming two of functional group in one-step reaction.This paper describes two parts of the research,including the chloroazidation and alkoxychlorination in the difunctionalization of alkenes.In this study,the azidation in the difunctionalization of olefins was realized by transition metal copper catalysis.We using Zhdankin's reagent as azidation reagent to construct chloroazides via copper catalyzed three component reaction of a,p-unsaturated amides under mild reaction conditions.We obtained 18 novel chloroazidation compounds through this mild and efficient method with high yield up to 90%.It is suitable for most ?,?-unsaturated amide and ester substrate.It is also proved that the product has strong applicability through a series of derivations of chloroazides products and an excellent yield can also be obtained on a gram-scale.Finally,we explored the mechanism and speculated that may lead to free radical addition reaction after CIN3 is produced by copper catalysis.In addition to the above chloroazidation reaction,we found another reation of alkenes with tetrahydrofuran which could provide a series of alkoxychlorination products.After optimization of conditions,we developed a method for the cohalogenation of ?,?-unsaturated amides using 1-Chloro-1,2-benziodoxol-3-(1H)-one as a chlorinating agent with excellent yields.A study on the substrate scope of this transformation proved it is suitable for the most of five-membered ?,?-unsaturated cyclic amides.We also need to study the scope of substrates,the selectivity and the scope of application of this reaction in the future.In this paper,our research focused on the difunctionalization of olefins.A series of novel amide compounds are obtained by using the cyclic hypervalent iodine reagents for atom-transfer reactions for azidation and chlorination of alkenes.