叔膦催化的一些用于构建五元或六元环化合物的环化反应研究

第Ⅱ页华东理工大学博士学位论文The Researches on Annulations Catalyzed by Tertiary Phosphines toConstruct Five or Six-Membered Ring CompoundsAbstractRecently,due to the fact that a wide variety of compounds can be synthesized simply andefficiently by phosphine-mediated reactions,the organic reactions catalyzed by tertiaryphosphines have been quickly developing.In the same time,the asymmetric reactionscatalyzed by chiral phosphines have also become an important method for the synthesis ofchiral compounds.This dissertation mainly focuses on the discovery of some newphosphine-catalyzed annulations and the realization of their asymmetric version,which isdivided into three parts.Part 1:Tertiary phosphines-catalyzed asymmetric annulations of MBH carbonates orallenoates with dicyano-activated conjugated dienes.(1)A novel [4+1]annulations of MBHcarbonates with dicyano-2-methylenebut-3-enoates has been discovered.Through the design,synthesis and screening of chiral phosphine catalysts,its asymmetric version has also beenrealized catalyzed by multifunctional thiourea-phosphine derived from chiral binaphthylscafford,providing an efficient and enantioselective synthesis of highly functionalizedcyclopentenes bearing one all-carbon quaternary stereogenic center.This is also the firstasymmetric [4+1]annulations of MBH carbonates.(2)Dicyano-activated conjugated dienesas a new a-substituted acrylates are employed in the phosphine-catalyzed [3+2]cycloadditionwith allenoates for the first time.The multifunctional chiral thiourea-phosphines having anaxially chiral binaphthyl scaffold are effective catalysts for the asymmetric variant of thisreaction,giving the corresponding products in good yields and moderate enantioselectivities.Part 2:The multifunctional chiral phosphines-catalyzed asymmetric Rauhut-Currierreactions.(1)Two highly nucleophilic multifunctional chiral phosphines have beensynthesized,and one of them has been successfully applied in enantioselective intramolecularRC reaction of two different bis(enone)s,giving the corresponding cyclopentene derivativesin good to excellent yields and good to excellent enantioselectivities and cyclohexenederivatives in moderate to good yields and good to excellent enantioselectivities,respectively.(2)An phosphine-catalyzed asymmetric [4+2]annulation reaction of vinyl ketones withoxindole-derived a,B-unsaturated imines has been developed for the first time to give thecorresponding isatin-based spiro-fused six-membered heterocycle derivatives.Two groups ofdifferent oxindole-derived a,B-unsaturated imines have been catalyzed respectively by two