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Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis

Shinichi Itsuno (Editor)
ISBN: 978-0-470-56820-0
528 pages
September 2011
Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis (0470568208) cover image
This book reviews chiral polymer synthesis and its application to asymmetric catalysis. It features the design and use of polymer-immobilized catalysts and methods for their design and synthesis. Chapters cover peptide-catalyzed and enantioselective synthesis, optically-active polymers, and continuous flow processes. It collects recent advances in an important field of polymer and organic chemistry, with leading researchers explaining applications in academic and industry R & D.
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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

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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.
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