Regiocontrolled Reductive Vinylation Of 1,3-Dienes By Nickel Catalysis

Transition-metal catalyzed hydrofunctionalization of 1,3-dienes has emerged as one of powerful methods to access molecular with complicated structure.In particular,hydrocarbonation reactions provide alternative for constructing vinyl-containing frameworks.Highly regiocontrolled 1,2-hydrocarbonation of conjugated dienes by using carbon nucleophiles have marked as a formidable advance in recent years.The chemo-,regio-and stereoselectivities in diene chemistry are well-controlled by the use of appropriate ligands.In comparison,the reactions including electrophiles are rarely reported in this line.Herein,we have focused on the development of highly regioselective 1,2-addition between vinyl electrophiles and 1,3-dienes.If it is successful,it thus offers a new selectivity pattern in this field.This manuscript included the following three sections:Section Ⅰ: The development of diene chemistry is still suffering the enormous challenges.We have summarized the progress in transition-metal catalyzed 1,2-hydrocarnonation between conjugated dienes and various carbon coupling reagents.Section Ⅱ: Under the mild reduction conditions,the combination of Ni（0）and phosphine-nitrile ligand has successfully resulted in branch-selective 1,2-hydrovinylation of aliphatic/aromatic 1,3-dienes with vinyl triflates.This reaction promotes with good functional group tolerance and broad substrate scope,which provides a novel method to access polyene molecules.Section Ⅲ: Based on the previous work,we have explored the linear-selective 1,2-additon pattern of above two substrates.The regioseletivity of aromatic dienes could be highly controlled in this transformation by the using of Py-BOX ligand,which affording corresponding 1,5-diene derivatives in promising yield.However,for aliphatic dienes,such reaction have failed to generate pure product.The regioisomers of linear selective1,2-and 1,4-adducts were detected in this transformation.