介孔有机硅纳米材料的制备及其在串联反应中的研究与应用-有机化学专业论文.docx

上海师范大学硕士学位论文Abstract 上海师范大学硕士学位论文 Abstract 万方数据 万方数据 silica, whilst a N-sulfonylateddiamine-based organoruthenium-functionality is easily anchored within ethylene-coated magnetic nanoparticles. The dual-immobilization approach efficiently eliminates the interactions of the two distinct organometallic complexes and overcomes their incompatibility. At last, the strategy done in the present study is based on a co-condensation method, where the site-isolated organopalladium-functionality and N-sulfonylated diamine-based organoruthenium-functionality are immobilized within a single periodic mesoporous organosilica. Such a strategy eliminates the interactions between the organometallic complexes and thereby overcomes their incompatibility. As expected, the Ru/Pd-bifunctionalized PMO efficiently catalyzed one-pot cascade asymmetric transfer hydrogenation and Suzuki cross-coupling of haloacetophenones and arylboronic acids to various chiral biaryl alcohols in aqueous medium. (2) Chiral β-hydroxy sulfones are a kind of important optically active alcohols, which are essential building blocks for several bioactive molecules. Because of electron withdrawing property of sulfonyl group at the β-position, the α-carbon could be further functionalized and sulfonyl group could be removed without racemization. For now, asymmetric reduction of β-keto sulfones is a common way to get chiral β-hydroxy sulfones. Though high yields and enantioselectivities were attained, the high pressure of reactions made them difficult to be operated. However, pure β-keto sulfones have to be obtained most of reported processes, which needs long production cycle and high cost of products. So, we design a novel catalytic procedure for one-pot, two-step synthesis of optically active β-hydroxy sulfones from α-bromoketones and sodium sulfinates in aqueous medium. Keywords: Cascade reactions; Suzuki cross-coupling reaction; Asymmetric transfer hydrogenation; Heterogeneous catalyst; Biaryl alcohols; Chiral β-hyd