Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis

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.

Auteur
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.

Contenu
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 Garca-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 Conclusio...