Study On The Selectivity Difunctionalization Of 1,3-Dienes

Difunctionalization of alkenes is an important reaction in organic chemistry,which can not only synthesize multi-site products in a cost-effective manner,but also convert the starting materials into a variety of chemical intermediates containing biological or pharmaceutical activities.It also provides efficient method for constructing the diversity of chemical structures.Thus,the development of new approach for difunctionalization of olefins is very important.Difunctionalization of 1,3-dienes has multiple reaction sites,it can obtain functionalized products with different double bonds,which also can be continued to modify by various methods to obtain polyfunctionalized products due to an unsaturated olefin double bond.As a result,it is necessary and significant to study the difunctionalization of 1,3-dienes.Difunctionalization of 1,3-dienes with high regioselectivity and stereoselectivity is also a challenge.The chemists mainly focus on the selective control of 1,2-difunctionalization and synthesis of（Z）-isomer products with transition metal catalysts（such as palladium,copper,nickel,etc.）.However,selective control of 1,4-difunctionalization and synthesis of（E）-isomer products are few reported.Therefore,we do some reserch on the difunctionalization of 1,3-dienes.This manuscript includes the following:In chapter 1,the advance in the 1,4-difunctionalization and 1,2-difunctionalization of 1,3-dienes in recent years was reviewed.In chapter 2,an indium salts controlled 1,4-alkylarylation of 1,3-dienes withα-carbonyl alkyl bromides and N-heterocycles was descried.After screened the Lewis acids,we found that InBr₃ was the best catalyst to achieve 1,4-alkylarylation with high regioselectivity and stereoselectivity.A series of 1,3-dienes were reacted withα-carbonyl alkyl bromides and N-heterocycles to afford the corresponding products in moderate yields with high selectivity under the reaction conditions.In chapter 3,a copper-catalyzed 1,4-trifluorocarboamination and 1,4-trifluorocarboarylation between 1,3-dienes and 1-trifluoro Methyl-1,2-benziodoxol-3（1H）-one with amines was realized.The results of the experiment showed that the following reaction types can be achevied by change the catalysts:（1）1,4 site C-H/C-H reaction with arylamines;（2）1,4 site C-H/N-H reaction with arylamines.This transformation features good functional group tolerance.We also proposed a possible reaction mechanism based on the control experiments.