Nickel-Catalyzed Electrophilic Iminoacylation And Alkylacylation Of Alkenes

In recent years,the in-depth study of cross-electrophile coupling reactions successfully expands their scope to electrophilic difunctionalizations of alkenes.Since preparation of organometallic reagents or organoborons can be avoided in cross'electrophile coupling,it is distinguished by high step economy,high functional group compatibility and mild reaction conditions.This reaction provides a new method for the synthesis of complex molecules and has received extensive attention from organic chemists.The installation of acyl group onto the olefinic unit of alkenes using acid chlorides or anhydrides as the acyl source constitutes an important subset of electrophilic difunctionalizations of alkenes.This dissertation firstly introduces the research progress of acylation reactions through cross-electrophile coupling reactions and olefin electrophilic difunctionalization reactions.In the second chapter,we develop a nickel-catalyzed electrophilic imino-acylation reaction of tethered alkenes.By use of a nickel/quinoline catalyst system,oxime esters bearing a pendant olefinic unit and acid chlorides or acid anhydrides are utilized as the substrates in assistance of zinc powder as the reducing agent,efficiently synthesizing a series of pyrroline derivatives under mild conditions.Compared with the previously reported method,this work is more desirable from the viewpoint of safety,operational simplicity and step-economy through bypassing the use of carbon monoxide gas and pregenerated organoborons.Besides,most of the acid chlorides or acid anhydrides used in these reactions are commercially available.Furthermore,this dissertation also establishes a strategy for efficient synthesis of ketones through nickel-catalyzed three-component alkyl-acylation of electron-deficient alkenes.This method features a broad substrate scope and high compatibility of a wide range of functional groups.The pertinent electron-deficient alkenes include alkenyl esters,alkenyl amides,alkenyl ketones,alkenyl sulfones and styrenes.Both aromatic and aliphatic acid anhydrides can be employed as the precursors.More importantly,this method can also be applied to 1,1-disubstituted alkenes.Following this protocol.diverse ketones containing a quaternary carbon center are obtained.Relying on nickel-catalyzed cross-electrophile coupling reactions,we realize two-component and three-component electrophilic acylation reactions of alkenes,respectively,which provide a new entry to syntheze complex pyrrolines and ketones.These reactions also suffer from a set of issues,which need to be resolved through more in-depth research.