Pd-Catalyzed Asymmetric Allylation Reactions Using Olefins And Allylic Alcohols As Allylating Substrates

π-allyl palladium complexes are among the most important immediates in organic synthesis. Due to a large number of nucleophiles capable of undergoing reactions with them, π-allyl palladium complexes were involved in a variety of transforms, allowing them to play a crucial role in palladium catalysis. Aside from the very common and useful allyl fragment containing an active leaving group, there are many other allylic precursors which can generate the π-allyl palladium complexes. These alternatives do not only enrich the categories of allylic alkylation reactions catalyzed by palladium, but also lead to either step-economic or environment sustainable allylic reactions. This thesis describes the creaction of some palladium-catalyzed asymmetric transformations using allylic alcohols, alkenes and 1,3-dienes as allylating reagents.The asymmetric allylic alkylation reaction of pyrazol-5-ones with allylic alcohols has been established under the cooperative catalysis of a palladium complex of chiral phosphoramidite ligand and a chiral phosphoric acid, affording the corresponding products containing an all-carbon quaternary stereogenic center in high yields and with excellent enantioselectivities. In comparison with classical Truji-Trost reaction, the allylic alkylation reaction directly using the allylic alcohols as substrates is more step-economic and environment-benign because water is the only byproduct.A highly stereoselective allylation of aldehydes with simple acyclic alkenes has been created in the presence of diborate and N-fluorobenzenesulfonimide (NSFI) under the catalysis of palladium complex and phosphoric acid. The reaction is a cascade process including a palladium-catalyzed allylic C-H borylation and an allylation of aldehydes. In this case, the oxidant plays a key role in the realization of the allylic C-H activation. The Brensted acid was able to promote the carbonyl allylation reaction and hence to facilitate the whole process. In addition, the enantioselective reaction was primarily investigated by using chiral Br(?)nsted acids to result in a moderate enantiomeric excess.A highly regio-and enantioselective multicomponent reaction of 1,3-butadienes, aryldiazonium tetrafluoroborates and aldehydes has been successfully developed in presence of octaphenyl-2,2’-bi(1,3,2-dioxaborolane), favoring the generation of Z-homoallylic alcohols in high yields, by using combined catalysis of palladium complex and chiral anion phase transfer. The reaction is actually a sequential process consisting of a Pd-catalyzed arylative allylic borylation of 1,3-diene and a carbonyl allylboration.