Single-Chain Folding of Polymers for Catalytic Systems in Water

被引:366
作者
Terashima, Takaya [1 ]
Mes, Tristan [1 ]
De Greef, Tom F. A. [1 ]
Gillissen, Martijn A. J. [1 ]
Besenius, Pol [1 ]
Palmans, Anja R. A. [1 ]
Meijer, E. W. [1 ]
机构
[1] Eindhoven Univ Technol, Inst Complex Mol Syst, Lab Macromol & Organ Chem, Biol Chem Lab, NL-5600 MB Eindhoven, Netherlands
关键词
ASYMMETRIC TRANSFER HYDROGENATION; STAR POLYMERS; ENANTIOSELECTIVE REDUCTION; HOMOGENEOUS CATALYSIS; KETONES; DENDRIMERS; CORE; NANOPARTICLES; PROTEINS; ALCOHOLS;
D O I
10.1021/ja2004494
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Enzymes are a source of inspiration for chemists attempting to create versatile synthetic catalysts. In order to arrive at a polymeric chain carrying catalytic units separated spatially, it is a prerequisite to fold these polymers in water into well-defined compartmentalized architectures thus creating a catalytic core. Herein, we report the synthesis, physical properties, and catalytic activity of a water-soluble segmented terpolymer in which a helical structure in the apolar core is created around a ruthenium-based catalyst. The supramolecular chirality of this catalytic system is the result of the self-assembly of benzene-1,3,5-tricarboxamide side chains, while the catalyst arises from the sequential ruthenium-catalyzed living radical polymerization of the different monomers followed by ligand exchange. The polymers exhibit a two-state folding process and show transfer hydrogenation in water.
引用
收藏
页码:4742 / 4745
页数:4
相关论文
共 32 条
[1]   "Microencapsulated" and Related Catalysts for Organic Chemistry and Organic Synthesis [J].
Akiyama, Ryo ;
Kobayashi, Shu .
CHEMICAL REVIEWS, 2009, 109 (02) :594-642
[2]   Asymmetric Transfer Hydrogenation of Aromatic Ketones in Water using a Polymer-Supported Chiral Catalyst Containing a Hydrophilic Pendant Group [J].
Arakawa, Yukihiro ;
Chiba, Atsuko ;
Haraguchi, Naoki ;
Itsuno, Shinichi .
ADVANCED SYNTHESIS & CATALYSIS, 2008, 350 (14-15) :2295-2304
[3]   Using Soluble Polymer Supports To Facilitate Homogeneous Catalysis [J].
Bergbreiter, David E. ;
Tian, Jianhua ;
Hongfa, Chayanant .
CHEMICAL REVIEWS, 2009, 109 (02) :530-582
[4]   DNA-based asymmetric catalysis: Sequence-dependent rate acceleration and enantioselectivity [J].
Boersma, Arnold J. ;
Klijn, Jaap E. ;
Feringa, Ben L. ;
Roelfes, Gerard .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (35) :11783-11790
[5]   A modular approach toward functionalized three-dimensional macromolecules:: From synthetic concepts to practical applications [J].
Bosman, AW ;
Vestberg, R ;
Heumann, A ;
Fréchet, JMJ ;
Hawker, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (03) :715-728
[6]   About dendrimers: Structure, physical properties, and applications [J].
Bosman, AW ;
Janssen, HM ;
Meijer, EW .
CHEMICAL REVIEWS, 1999, 99 (07) :1665-1688
[7]   One-pot multi-component asymmetric cascade reactions catalyzed by soluble star polymers with highly branched non-interpenetrating catalytic cores [J].
Chi, Yonggui ;
Scroggins, Steven T. ;
Frechet, Jean M. J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (20) :6322-+
[8]   Metastable Supramolecular Polymer Nanoparticles via Intramolecular Collapse of Single Polymer Chains [J].
Foster, E. Johan ;
Berda, Erik B. ;
Meijer, E. W. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (20) :6964-+
[9]   How enzymes work: Analysis by modern rate theory and computer simulations [J].
Garcia-Viloca, M ;
Gao, J ;
Karplus, M ;
Truhlar, DG .
SCIENCE, 2004, 303 (5655) :186-195
[10]   Convergent dendrons and dendrimers:: from synthesis to applications [J].
Grayson, SM ;
Fréchet, JMJ .
CHEMICAL REVIEWS, 2001, 101 (12) :3819-3867