1,1'-binaphthyl-based Chiral Materials: Our Journey

by Lin Pu

Overview

Chiral materials have been studied in the Department of Chemistry at the University of Virginia for applications in areas like asymmetric catalysis, enantioselective fluorescent sensing, and optical/electrical materials. Optically active 1,1′-binaphthyl molecules are used to build novel chiral polymers, dendrimers, macrocycles, and acyclic molecules. 1,1′-Binaphthyl molecules are chosen because of their remarkably stable chiral configuration as well as their high asymmetric inductions in many processes.In this book, both the fundamental knowledge about the 1,1′-binaphthyl molecules and the synthesis of the structurally diverse 1,1′-binaphthyl-based materials are described. The applications of these materials in various fields are also discussed. This book will serve as a reference for graduate students as well as other professionals working in the related fields.

Product Details

ISBN-13:	9781848164116
Publisher:	Imperial College Press
Publication date:	08/17/2009
Pages:	368
Product dimensions:	5.90(w) x 9.10(h) x 1.00(d)

Table of Contents

Preface v

1 Introduction About l,l'-Binaphthyls 1

References 10

2 Main Chain Chiral-Conjugated Polymers 13

2.1 Introduction About Chiral-Conjugated Polymers 13

2.2 Binaphthyl-Based Polyarylenevinylenes 17

2.3 Binaphthyl-Based Polyarylenes 20

2.4 Binaphthyl-Based Polyaryleneethynylenes 23

2.5 Binaphthyl-Thiophene Copolymers 30

2.6 Copolymers of BINAM and Thiophene-Containing Conjugated Linkers 37

2.7 Polybinaphthyls Without Conjugated Linkers 39

2.8 Propeller-Like Polybinaphthyls 51

2.9 Dipole-Oriented Propeller-Like Polymers 69

2.10 Binaphthyl-Based Polysalophens 71

2.11 Helical Ladder Polybinaphthyls 76

References 85

3 Polybinaphthyls in Asymmetric Catalysis 87

3.1 Introduction about Chiral Polymers in Asymmetric Catalysis 87

3.2 Synthesis of Major-Groove Poly (BINOL)s 89

3.3 Application of the Major-Groove Poly (BINOL)s to Catalyze the Mukaiyama Aldol Reaction 95

3.4 Application of the Major-Groove Poly (BINOL)s to Catalyze the Hetero-Diels-Alder Reaction 99

3.5 Using the Ti(IV) Complex of the Major-Groove Poly (BINOL) to Catalyze the Diethylzinc Addition to Aldehydes 101

3.6 Synthesis of the Minor-Groove Poly (BINOL)s 102

3.7 Application of the Major- and Minor-Groove Poly (BINOL)s to Catalyze the Asymmetric Organozinc Addition to Aldehydes 105

3.8 Asymmetric Reduction of Prochiral Ketones Catalyzed by the Chiral BINOL Monomer and Polymer Catalysts 122

3.9 Asymmetric Epoxidation of α,β-Unsaturated Ketones Catalyzed by the Minor- and Major-Groove Poly (BINOL)s 125

3.10 Asymmetric Diels-Alder Reaction Catalyzed by Poly (BINOL)-B (III) Complexes 133

3.11 1,3-Dipolar Cycloaddition Catalyzed by the Minor- and Major-Groove Poly(BINOL)-A1(III) Complexes 136

3.12 Asymmetric Michael Addition Catalyzed by the Poly (BINOL)s 139

3.13 Synthesis and Study of Poly (BINAP) 141

3.14 Synthesis and Study of a BINOL-BINAP Copolymer 146

References 150

4 Asymmetric Catalysis by BINOL and Its Non-polymeric Derivatives 151

4.1 Introduction 151

4.2 Asymmetric Alkyne Additions to Aldehydes 151

4.3 Asymmetric Arylzinc Addition to Aldehydes 198

4.4 Asymmetric Alkylzinc Addition to Aldehydes 216

4.5 Asymmetric TMSCN Addition to Aldehydes 225

4.6 Asymmetric Hetero-Diels-Alder Reaction 233

References 235

5 Enantioselective Fluorescent Sensors Based on l,l'-Binaphthyl-Derived Dendrimers, Small Molecules and Macrocycles 239

5.1 Introduction 239

5.2 Using Phenyleneethynylene-BINOL Dendrimers for the Recognition of Amino Alcohols 240

5.3 Using Phenylene-BINOL Dendrimers for the Recognition of Chiral Amino Alcohols 246

5.4 Using Functionalized BINOLs for the Recognition of Amino Alcohols and Amines 252

5.5 Using Acyclic Bisbinaphthyls for the Recognition of α-Hydroxycarboxylic Acids and Amino Acid Derivatives 257

5.6 Using Diphenylethylenediamine-BINOL Macrocycles for the Recognition of α-Hydroxycarboxylic Acids 263

5.7 Using Cyclohexanediamine-BINOL Macrocycles and Their Derivatives for the Recognition of α-Hydroxycarboxylic Acids and Amino Acid Derivatives 282

5.8 Application of the Cyclohexanediamine-BINOL Macrocycle Sensor in Catalyst Screening³¹ 294

5.9 Using Monobinaphthyl Compounds for the Recognition of α-Hydroxycarboxylic Acids and Amino Acid Derivatives 299

5.10 Enantioselective Precipitation and Solid-State Fluorescence Enhancement in the Recognition of α-Hydroxycarboxylic Acids by Using Monobinaphthyl Compounds 303

References 308

6 Miscellaneous Studies on Materials Related to l,l'-Binaphthyls 311

6.1 Chiral Molecular Wires 311

6.2 A Biphenol Polymer 316

6.3 Supramolecular Chemistry of Self-Assembly of Racemic and Optically Active Propargylic Alcohols 318

References 331

Index 333