Nickel-Catalyzed Regioselective Arylboration Of 1,3-Dienes

In metal-organic chemistry,the difunctionalization of 1,3-diene is an effective strategy for the synthesis of many important compounds,and the carboration of 1,3-diene is one of the most active research areas.In this field,the alkylboration of 1,3-diene has achieved great progress in recent years,and chemists have constructed a series of boron-containing compounds through this strategy.However,the reports about the arylboration of 1,3-diene are still quite limited,mainly for Palladium/copper co-catalytic strategy.Therefore,we need to explore the single-metal-catalyzed arylboration of 1,3-dienes urgently.The transition metal nickel-catalyzed regioselective arylboration of 1,3-dienes is reported in this work.Good 1,4-regioselectivity and（E）-stereoselectivity were obtained using isoprene,together with very good 1,2-regioselectivity and（E）-stereoselectivity using 1-aryl-1,3-dienes.The high reactivity and selectivity of this process were dependent on the use of the appropriate nitrogen-based ligand.Moreover,wide functional group tolerance was observed under mild reaction conditions.This protocol provides a path to allyl or homoallyl boronic ester derivatives starting from 1,3-dienes,aryl bromides,and B₂pin₂.The downstream transformation of allyl boronic esters was also achieved,suggesting a strategy for the diastereoselective 1,2-difunctionalization of isoprene and demon-strating the potential for the synthesis of complex molecules.