Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis

Shinichi Itsuno, PhD , is a Professor at Toyohashi University of Technology. His research focuses on the interface between organic chemistry and polymer chemistry, and is especially concerned with asymmetric synthesis, reactive polymers, and new polymer synthesis. Dr. Itsuno has written over a hundred papers, as well as thirty book chapters.

PREFACE xiii FOREWORD xvii CONTRIBUTORS xix 1 An Overview of Polymer-Immobilized Chiral Catalysts and Synthetic Chiral Polymers 1 Shinichi Itsuno 1.1 Introduction / 1 1.2 Polymeric Chiral Catalyst / 2 1.3 Synthesis of Optically Active Polymers / 8 2 Polymer-Immobilized Chiral Organocatalyst 17 Naoki Haraguchi and Shinichi Itsuno 2.1 Introduction / 17 2.2 Synthesis of Polymer-immobilized Chiral Organocatalyst / 18 2.3 Polymer-immobilized Cinchona Alkaloids / 22 2.4 Other Polymer-immobilized Chiral Basic Organocatalysts / 27 2.5 Polymer-immobilized Cinchona Alkaloid Quaternary Ammonium Salts / 28 2.6 Polymer-immobilized MacMillan Catalysts / 35 2.7 Polymer-immobilized Pyrrolidine Derivatives / 42 2.8 Other Polymer-immobilized Chiral Quaternary Ammonium Salts / 46 2.9 Polymer-immobilized Proline Derivatives / 46 2.10 Polymer-immobilized Peptides and Poly(amino acid)s / 50 2.11 Polymer-immobilized Chiral Acidic Organocatalysts / 50 2.12 Helical Polymers as Chiral Organocatalysts / 51 2.13 Cascade Reactions Using Polymer-immobilized Chiral Organocatalysts / 52 2.14 Conclusions / 54 3 Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives 63 Michelangelo Gruttadauria, Francesco Giacalone, and Renato Noto 3.1 Introduction / 63 3.2 Polymer-supported Proline / 66 3.3 Polymer-supported Prolinamides / 73 3.4 Polymer-supported Proline-Peptides / 75 3.5 Polymer-supported Pyrrolidines / 78 3.6 Polymer-supported Prolinol and Diarylprolinol Derivatives / 80 3.7 Conclusions and Outlooks / 84 4 Peptide-Catalyzed Asymmetric Synthesis 91 Kazuaki Kudo and Kengo Akagawa 4.1 Introduction / 91 4.2 Poly(amino acid) Catalysts / 94 4.3 Tri- and Tetrapeptide Catalysts / 99 4.4 Longer Peptides with a Secondary Structure / 110 4.5 Others / 118 4.6 Conclusions and Outlooks / 119 5 Continuous Flow System using Polymer-Supported Chiral Catalysts 125 Santiago V. Luis and Eduardo Garcia-Verdugo 5.1 Introduction / 125 5.2 Asymmetric Polymer-supported, Metal-based Catalysts and Reagents / 132 5.3 Polymer-supported Asymmetric Organocatalysts / 147 5.4 Polymer-supported Biocatalysts / 151 5.5 Conclusions / 152 6 Chiral Synthesis on Polymer Support: A Combinatorial Approach 157 Deepak B. Salunke and Chung-Ming Sun 6.1 Introduction / 157 6.2 Chiral Synthesis of Complex Polyfunctional Molecules on Polymer Support / 160 6.3 Conclusions / 194 7 Synthesis and Application of Helical Polymers with Macromolecular Helicity Memory 201 Hiroki Iida and Eiji Yashima 7.1 Introduction / 201 7.2 Macromolecular Helicity Memory / 203 7.3 Enantioselective Reaction Assisted by Helical Polymers with Helicity Memory / 218 7.4 Conclusions / 219 8 Poly(isocyanide)s, Poly(quinoxaline-2,3-diyl)s, and Related Helical Polymers Used as Chiral Polymer Catalysts in Asymmetric Synthesis 223 Yuuya Nagata and Michinori Suginome 8.1 Introduction / 223 8.2 Asymmetric Synthesis of Poly(isocyanide)s / 224 8.3 Asymmetric Synthesis of Poly(quinoxaline)s / 244 8.4 Enantioselective Catalysis using Helical Polymers / 255 8.5 Conclusions / 262 9 C2 Chiral Biaryl Unit-Based Helical Polymers and Their Application to Asymmetric Catalysis 267 Takeshi Maeda and Toshikazu Takata 9.1 Introduction / 267 9.2 Synthesis of C2 Chiral Unit-based Helical Polymers / 269 9.3 Asymmetric Reactions Catalyzed by Helical Polymer Catalysts / 282 9.4 Conclusions / 289 10 Immobilization of Multicomponent Asymmetric Catalysts (MACs) 293 Hiroaki Sasai and Shinobu Takizawa 10.1 Introduction / 293 10.2 Dendrimer-Supported and Dendronized Polymer-supported MACs / 294 10.3 Nanoparticles as Supports for Chiral Catalysts [13] / 302 10.4 The Catalyst Analog Approach [24] / 311 10.5 Metal-bridged Polymers as Heterogeneous Catalysts: An Immobilization Method for MACs Without Using Any Support [26] / 314 10.6 Conclusion / 318 11 Optically Active Polymer and Dendrimer Synthesis and Their Use in Asymmetric Synthesis 323 Qiao-Sheng Hu and Lin Pu 11.1 Introduction / 323 11.2 Synthesis and Application of BINOL/BINAP-based Optically Active Polymers / 324 11.3 Synthesis and Application of Optically Active Dendrimers / 355 11.4 Conclusions / 360 12 Asymmetric Polymerizations of N -Substituted Maleimides 365 Kenjiro Onimura and Tsutomu Oishi 12.1 Introduction / 365 12.2 Chirality of 1-Mono- or 1,1-Disubstituted and 1,2-Disubstituted Olefins / 365 12.3 Asymmetric Polymerizations of Achiral N-Substituted Maleimides / 368 12.4 Anionic Polymerization Mechanism of RMI / 371 12.5 Asymmetric Polymerizations of Chiral N-Substituted Maleimides / 372 12.6 Structure and Absolute Stereochemistry of Poly(RMI) / 373 12.7 Asymmetric Radical Polymerizations ofN-Substituted Maleimides / 378 12.8 Chiral Discrimination Using Poly(RMI) / 378 12.9 Conclusions / 384 13 Synthesis of Hyperbranched Polymer Having Binaphthol Units via Oxidative Cross-Coupling Polymerization 389 Shigeki Habaue 13.1 Introduction / 389 13.2 Oxidative Cross-coupling Reaction between 2-Naphthol and 3-Hydroxy-2-naphthoate / 391 13.3 Oxidative Cross-coupling Polymerization Affording Linear Poly(binaphthol) / 392 13.4 Oxidative Cross-coupling Polymerization Leading to a Hyperbranched Polymer / 396 13.5 Photoluminescence Properties of Hyperbranched Polymers / 400 13.6 Conclusions / 403 14 Optically Active Polyketones 407 Kyoko Nozaki 14.1 Introduction / 407 14.2 Asymmetric Synthesis of Isotactic Poly(propylene-alt-co) / 409 14.3 Asymmetric Synthesis of Isotactic Syndiotactic Poly(styrene-alt-co) / 411 14.4 Asymmetric Terpolymers Consisting of Two Kinds of Olefins and Carbon Monoxide / 413 14.5 Asymmetric Polymerization of Other Olefins with CO / 414 14.6 Chemical Transformations of Optically Active Polyketones / 415 14.7 Conformational Studies on the Optically Active Polyketones / 416 14.8 Conclusions / 419 15 Synthesis and Function of Chiral p -Conjugated Polymers from Phenylacetylenes 423 Toshiki Aoki, Takashi Kaneko, and Masahiro Teraguchi 15.1 Introduction / 423 15.2 Helix-sense-selective Polymerization (HSSP) of Substituted Phenylacetylenes and Function of the Resulting One-handed Helical Poly(phenylacetylene)s / 425 15.3 Chiral Desubstitution of Side Groups in Membrane State / 439 15.4 Synthesis of Chiral Polyradicals / 446 16 P-Stereogenic Oligomers, Polymers, and Related Cyclic Compounds 457 Yasuhiro Morisaki and Yoshiki Chujo 16.1 Introduction / 457 16.2 P-Stereogenic Oligomers Containing Chiral "P" Atoms in the Main Chain / 458 16.3 P-Stereogenic Polymers Containing Chiral "P" Atoms in the Main Chain / 470 16.4 Cyclic Phosphines Using P-Stereogenic Oligomers as Building Blocks / 475 16.5 Conclusions / 485 INDEX 489