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Synthesis Of Zirconium Phosphonate-Supported Chiral Pd(Binap)Cl2 Catalysts And Application In The Heterogeneous Asymmetric Suzuki Reaction

Posted on:2011-05-30Degree:MasterType:Thesis
Country:ChinaCandidate:Y Y MaFull Text:PDF
GTID:2181360302497855Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
Suzuki-Miyaura cross-coupling reaction has received considerable attention in the field of catalysis now. In this thesis, chiral Pd(Binap)Cl2 complex was immobilized successfully onto the frame of zirconimu phosphonate via ion pair by sulfonic group with different linkage arm lengths, which made the heterogeneous catalysis of Suzuki-Miyaura cross-coupling reaction come true,In the paper, ten of zirconium phosphonate-supported palladium chiral catalysts 8a-e and 9a-e had been synthesised. The structure and morphorlogy of these catalysts had been characterized by using ICP-AES, IR, TG, XPRD, N2 adsorption-desorption isothermal curve and SEM, and chemical construction and structure, the supported mount of palladium had been determined.From XPRD, N2 adsorption-desorption isotherm, SEM images showed that this type of chiral palladium catalysts possessed the layered (intensity 15.98-18.94 A), mesoporous (pore volume 3.55-271.30×10-3 cc/g, surface area 0.37-15.29 m2/g) structure. The supported mount of palladium in catalysts 8a-e and 9a-e is in the range of 0.183-0.185%.In the heterogeneous asymmetric Suzuki-Miyaura cross-coupling, this novel type of zirconium phosphonate-supported chiral palladium catalyst possessed the high catalytic activities at 90℃for 2 h (83.2-99.8%yield and 35.4-67.3%e.e.). Furtheremore, the supported chiral palladium catalyst had the better catalytic properties than the corresponding homogeneous chiral palladium catalyst (72%yield and 24%e.e. of 2-methylbinaphthalene), which showed the existence of site isolation effect and confinement effect. After the reaction was completed, the supported chiral palladium catalysts were quantitatively recovered and reused without the sharp loss of catalytic activities for three times.
Keywords/Search Tags:Zirconium Phosphonate, Pd(Binap)Cl2 complex, Supported, Asymmetric Suzuki reaction
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