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Optically Active Helical Polyisocyanides Bearing Chiral Phosphine Pendants: Facile Synthesis and Application in Enantioselective Rauhut-Currier Reaction

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Chinese Journal of polymer Science 2018年第2期36卷 163-170页

作者： Li Zhou Ling Shen Jian Huang Na Liu Yuan-Yuan Zhu Zong-Quan Wu Department of polymer Science and Engineering School of Chemistry and Chemical Engineering and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering Hefei University of Technology School of Material and Chemical Engineering Bengbu University

Three novel enantiopure phenyl isocyanide monomers with BH3-protected phosphine functional group were designed and synthesized. polymerization of these monomers using a alkyne-Pd（II） complex as a catalyst led to the formation of respective helical polyisocyanides in high yields with controlled molecular weights（Mns） and narrow molecular weight distributions（Mw/Mns）. Removing the protecting BH3 groups afforded helical poly（phenyl isocyanide）s bearing phosphine pendants. Thanks to the chiral induction of monomer, the isolated helical polyisocyanides showed high optical activity, as revealed by circular dichroism（CD） and absorption spectroscopies and polarimetry. The helical structures of these polymers were quite stable in various organic solvents with different polarities and in a wide temperature range. Moreover, these helical polymers could be used as organocatalysts and showed good performance in enantioselective cross Rauhut-Currier reaction. The enantiomeric excess（ee） values of the isolated products of cross Rauhut-Currier reaction could be up to 90%. The polymer organocatalysts could be easily recovered from the reaction mixtures and reused at least five times in the reaction without significant loss of their enantioselectivities and catalytic activities.

关键词： Helical polymer Polyisocyanide Coordination polymerization polymer catalyst

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STUDY ON polymer—Ru-Co—BIMETALLIC COMPLEXES catalystS Ⅰ. SYNTHESIS OF catalystS AND THEIR USE FOR THE HYDROFORMYLATION

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Chinese Journal of polymer Science 1991年第1期9卷 39-47页

作者：汤琪宗惠娟陈宗翰江英彦 Institute of Chemistry Academia Sinica Beijing

Six kinds of polymer ligands, supported on SiO_2, containing coordinating atoms P, S and N respectively, have been synthesized. The Ru(Ⅲ)-Co(Ⅱ) bimetallic complexes of these polymer ligands have been obtained and examined as catalysts for the hydroformylation of cyclohexene. The effects of reaction temperature, pressure and Co/Ru ratio etc. on the activities of catalysts were investigated in detail. The catalysts are all polymer-noncarbonyl-metal complexes, easily to be prepared, active and stable. From the experimental results it can be suggested that under reaction conditions such polymer-noncarbonyl-metal complexes convert 'in situ' to polymer-carbonyl-metal complexes, thus become active catalysts. The course of this conversion is supposed as a preliminary approach.

关键词： polymer catalyst Bimetallic complex Cydohexene Hydroformylation

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THE SYNTHESIS,HYDROGENATION ACTIVITY AND STRUCTURAL CHARACTERIZATION OF POLY-γ- (L-GLYCYLALANINE) PROPYL SILOXANE PALLADIUM catalystS

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Wuhan University Journal of Natural Sciences 1998年第1期3卷 91-91页

作者： Chen Shihuang Liu Jiwan You Jiang Zhang Xiaohui Chemistry Department of Wuhan University Wuhan China Department of Environmental Protection Jianghan University Jianghan China

This paper describes the synthesis of poly-γ-(L-glycylalanine) propylsiloxane palladium catalysts withdifferent N/Pd molar ratios and their catalytic activity. XPS data of the title catalyst indicated that the active center may be complex compound composed of the -COOH and -NH2 of amino acid ligand and PdCl2. The hydrogenation activity of the title catalysts is very high for acrylonitrile,propenol and acrylic acid,but inactive for a-methyl acrylic acid and 1-decene. The influence of solvents,N/Pd molar tatio,and reaction temperature on catalytic hydrogenation of acrylonitrile was studied respectively.

关键词： polymer catalyst amino acid hydrogenation activity

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