Table of Contents
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 Garcıa-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
