Cu-catalyzed Dehydrogenative Borylation Of Terminal Alkenes With Pinacolborane

Alkenylboronates are versatile and universal intermediate in organic chemistry,pharmaceutical field and industrial material,which can be readily converted to a serial of functional groups such as C?C,C?O,C?N,C?F,C?Br and C?I bonds by transition metal-catalyzed cross-coupling reactions.Among reported extraordinary approaches,Suzuki-Miyaura reactions and Petasis reactions are the most typical methods for the transformation of organoboron reagents.Given the significance of alkenylboronats,chemists paid much attention to finding highly efficient approaches for the synthesis of alkenylboronats.In this thesis,we focus on copper-catalyzed dehydrogenative borylation of terminal alkenes with pinacolborane and 2-vinyl naphthalene as the substrate.Through the experimental exploration and optimization of conditions,we developed a simple and convenient method for the synthesis of alkenylboronats by using low cost copper salt,Cy John Phos ligand and TEMPO oxidant.For substrate scope,all kinds of substituted aryl alkenes as well as heterocyclic aryl alkenes show high compatibility under this catalytic system.In particular,aryl alkene containing estrone structure performed well under this catalytic system.A series of mechanistic studies reveal a new catalytic cycle and TEMPO plays a vital role in this catalytic cycle.In addition,we modified the original conditions applying for aryl alkenes to achieve the borylation of alkyl alkenes.