Studies On Enantioselective Ir-Catalyzed Allylic Alkylation Of Racemic Allylic Alcohols With Malonates

Transition metal-catalyzed asymmetric allylic alkylation reaction is one of the most important methods for the synthesis of chiral compounds.Iridium-catalyzed asymmetric allylic alkylation reactions have attracted intense attention due to their exceptionally regio-and enantioselectivities.At the same time,the strategy of Ir-catalyzed asymmetric allylic alkylation can achieve synthesis of many natural products,so this kind of reaction has certain practical significance and scientific research value.Studies on Ir-catalyzed asymmetric allylic alkylation is described in this thesis,and it consists of the following three chapters.In chapter 1,the recent research of Ir-catalyzed asymmetric allylic alkylation progress is introduced.In this review,we summarize the origin and advancements of Ir-catalyzed asymmetric allylic alkylation reactions during the past two decades.Since the first report in 1997,Ir-catalyzed asymmetric allylic alkylation reactions have attracted much attention because of their high regio-and enantioselectivities.Ir-catalyzed asymmetric allylic alkylation reactions have been significantly developed in recent years in many respects,including ligand development,substrate scope,and application in the synthesis.In chapter 2,enantioselective Ir-catalyzed allylic alkylation of racemic allylic alcohols with malonates is introduced.Ir-catalyzed enantioselective allylic alkylation of branched racemic allylic alcohols with malonates is described.Enabled by Carreira's chiral Ir/(P,olefin)complex,the method described allows allylic substitution with various aromatic alcohols and malonates with excellent enantioselectivity.The malonates could be used directly as efficient nucleophiles without the need of preactivation,branched allylic alcohols also do not need hydroxyl protection,the reaction is more environmentally friendly.In chapter 3,experimental procedures and spectra data of allylic compounds are recorded.