Reaction Studies On Construction Of Core Framework Oriented Chiral Centers And Phosphine-Catalyzed Asymmetric [3+2] Cycloaddition

This dissertation is mainly divided into three parts:chiral quaternary carbon centered construction based on benzofuranones or oxindoles skeleton; chiral spiro-posphine catalyzed asymmetric [3+2] annulation of allenoates with alkylidene azlactones or olefins derived from benzofuranones as cyclic electronic deficient olefins, the corresponding spiro compounds were obtained in good results, and the mechanism of in-depth also inquiry; highly efficient construction of trifluoromethylated heterocycles pyrazolidine and new method for synthesized indolinzine and further transformation.Part Ⅰ:Oxindole and benzofuranone framework oriented electrophilic and nucleophilic substituted reactionA novel asymmetric chlorination of3-substituted oxindoles was reported, affording the corresponding chlorinated adducts in good yields and up to88%ee value by using of axially chiral BINIM-Ni(II) complexes (Chapter1.1).We have established an efficient chiral phosphine-catalyzed asymmetric allylic alkylation of MBH carbonates with3-substituted benzofuran-2(3H)-ones or oxindoles to give the corresponding substitution products in high yields with moderate dr values and high ee values for major and minor diastereomeric products under mild conditions. As for benzofuran-2(3H)-ones, the desired products could be obtained in high yields with moderate diastereoselectivities (syn.anti) and excellent ee values for both major products and minor products. While as for oxindoles, the AAA reactions afforded the products in moderate to high yields (76-93%) with moderate diastereoselectivities (anti.syn) and good ee values for major products and minor products. A plausible mechanism for this asymmetric reaction is outlined (Chapter1.2).Part Ⅱ:A novel spiro phosphine catalyzed [3+2] cycloaddition reactionA novel spiro-phosphine-catalyzed highly regio-, diastereo-and enantioselective [3+2] cycloaddition of alkylidene azlactones with various allenic esters has been developed, affording the corresponding functionalized spirocyclic products in moderate to excellent yields under mild conditions. These spirocyclic products as masked amino acids can be easily transformed to aspartic amino acid analogues.(Chapter2.1). Catalytic asymmetric [3+2] cycloadditions of benzofuranone derived olefins wih different substituted allenoates catalyzed by (R)-SITCP have been developed, affording3-spirocyclopentene benzofuran-2-ones in good yields with high enantioselectivities and regioselectivities under mild condition. The DFT studies disclosed the origins of regioselective outcomes for this phosphine-catalyzed [3+2] reaction (Chapter2.2).Part Ⅲ:Construction of functionalized nitrogen heterocycles molecularsIn this part, two type of nitrogen containing heterocyclic moleculars were obtained under mild react conditions.We have developed a novel [3+2] annulation of N,N’-cyclic or C,N-cyclic azomethine imines with CF3-containing olefins, affording the corresponding trifluoromethyl-containing pyrazolidine analogues in excellent yields (up to>99%) with high diastereoselectivities (up to99:1) under mild conditions (Chapter3.1).We have developed a novel method for the construction of aminoindolizines by using of2-enoylpyridines and sulfonamides in moderate to high yields (60-95%) under mild conditions. The subsequent phosphine catalyzed aza-Michael addition reaction has also been developed to give the desired products in excellent yields (87-99%)(Chapter3.2).