Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis

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

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