1,1′-Binaphthyl-Based Chiral Materials

The following sections are included:

• Preface

• Contents

1,1'-Binaphthyl compounds represent a special class of biaryl molecules. For a simple unsubstituted biphenyl molecule, its rotation barrier around the phenyl–phenyl bond in gas phase was found to be ∼1.4 kcal/mol.¹ 1,1'-Binaphthyl incorporated with fused benzene rings to biphenyl has a greatly increased rotation barrier of 23.5 kcal/mol (ΔG^≠).² In addition, 1,1'-binaphthyl no longer possesses the plane of symmetry that biphenyl has at the orthogonal conformation. This allows the isolation of the optically active 1,1'-binaphthyl enantiomers. A chiral 1,1'-binaphthyl molecule contains a chiral axis instead of a chiral center. The racemization half-life of the optically active 1,1'-binaphthyl was 14.5min at 50°C. 1,1'-Binaphthyls have two possible racemization pathways. One goes through a syn interaction state where there are close contacts for the 2,2'-H's and 8,8'-H's, and another goes through an anti interaction state where there are close contacts for the 2,8'-H's and 2',8-H's. When theoretical rigid models are applied, the anti pathway gives lower steric hindrance than the syn route. Calculations show that 1,1'-binaphthyl favors the anti inversion racemization mechanism.^3,4 However, semi-empirical calculations suggest that 2,2'-dibromo-1,1'-binaphthyl should favor a multi-stage syn racemization pathway. The aromatic rings in the transition states of this racemization process are significantly distorted…

The following sections are included:

• Introduction About Chiral-Conjugated Polymers

• Binaphthyl-Based Polyarylenevinylenes

• Binaphthyl-Based Polyarylenes

• Binaphthyl-Based Polyaryleneethynylenes

• Binaphthyl–Thiophene Copolymers
  • Copolymerization of Binaphthyl and Oligothiophene Monomers
  • Electroluminescence Study

• Copolymers of BINAM and Thiophene-Containing Conjugated Linkers

• Polybinaphthyls Without Conjugated Linkers
  • Using Nickel Complexes to Promote Polymerization
  • Synthesis of the Binaphthyl-Based Polydendrimers by Using Ni Complexes to Promote Polymerization
  • Using the Suzuki Coupling Reaction for Polymerization
  • Electroluminescence Study of the Polybinaphthyls

• Propeller-Like Polybinaphthyls
  • Synthesis of the Propeller-Like Polymers Derived from BINOL
  • Synthesis of the Propeller-Like Polymers Derived from BINAM
  • Study of the Non-linear Optical Properties of the Propeller-Like Polymers

• Dipole-Oriented Propeller-Like Polymers

• Binaphthyl-Based Polysalophens

• Helical Ladder Polybinaphthyls

• References

The following sections are included:

• Introduction about Chiral Polymers in Asymmetric Catalysis

• Synthesis of Major-Groove Poly(BINOL)s
  • Synthesis of Polybinaphthyls with Various Protecting Groups
  • Hydrolysis of the Polybinaphthyls to Generate Poly(BINOL)s
  • Synthesis of Poly(BINOL)s Containing Alkyl-Substituted Phenylene Linkers

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

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

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

• Synthesis of the Minor-Groove Poly(BINOL)s

• Application of the Major- and Minor-Groove Poly(BINOL)s to Catalyze the Asymmetric Organozinc Addition to Aldehydes
  • Asymmetric Diethylzinc Addition to Aldehydes Catalyzed by the Poly(BINOL)s
  • Study of the Reactions of the Minor-Groove Poly(BINOL) and a Few Monomeric BINOL Derivatives with Diethylzinc
  • Synthesis of the Monomeric Model Compound of the Minor-Groove Poly(BINOL) to Catalyze the Dialkylzinc Addition to Aldehydes
  • Converting the Highly Enantioselective Mono(BINOL) Catalyst to a Highly Enantioselective Poly(BINOL) Catalyst for the Asymmetric Organozinc Additions

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

• Asymmetric Epoxidation of α,β-Unsaturated Ketones Catalyzed by the Minor- and Major-Groove Poly(BINOL)s
  • Asymmetric Epoxidation of α,β-Unsaturated Ketones in the Presence of a Stoichiometric Amount of the Major-Groove Poly(BINOL)s, Diethylzinc and Oxygen
  • Development of a Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ketones Using Poly(BINOL)s, Diethylzinc and t-Butyl Hydroperoxide
  • Asymmetric Epoxidation of α,β-Unsaturated Ketones by Using the Yb and La Complexes of Poly(BINOL)s

• Asymmetric Diels–Alder Reaction Catalyzed by Poly(BINOL)–B(III) Complexes

• 1,3-Dipolar Cycloaddition Catalyzed by the Minor-and Major-Groove Poly(BINOL)–Al(III) Complexes

• Asymmetric Michael Addition Catalyzed by the Poly(BINOL)s

• Synthesis and Study of Poly(BINAP)

• Synthesis and Study of a BINOL–BINAP Copolymer

• References

The following sections are included:

• Introduction

• Asymmetric Alkyne Additions to Aldehydes
  • Catalysis by BINOL–ZnEt₂–Ti(OⁱPr)₄
  • Catalysis by BINOL–ZnEt₂–Ti(OⁱPr)₄–HMPA and Functional Alkyne Addition
  • Reactivity of γ-Hydroxy-α, β-acetylenic Esters
  • Catalysis by 3,3'-Bisanisyl-Substituted BINOLs
  • Catalysis by 3,3'-Bis(diphenylmethoxy)methyl Substituted BINOLs
  • Catalysis by Acyclic and Macrocyclic Binaphthyl Salens
  • Catalysis by 3,3'-Bismorpholinomethyl H₈BINOL

• Asymmetric Arylzinc Addition to Aldehydes
  • Catalysis by the 3,3'-Bisanisyl-Substituted BINOLs
  • Catalysis by 3,3'-Bismorpholinomethyl-Substituted BINOL and H₈BINOL Ligands
  • Asymmetric Functional Arylzinc Addition Catalyzed by the 3,3'-Substituted BINOL and H₈BINOL Ligands

• Asymmetric Alkylzinc Addition to Aldehydes
  • Using the 3,3'-Diaryl-Substituted BINOL Ligands
  • Using the 3,3'-Morpholinomethyl-Substituted H₈BINOL Ligand
  • Using a Dendritic BINOL Ligand

• Asymmetric TMSCN Addition to Aldehydes
  • Catalysis by the 3,3'-Bismorpholinomethyl BINOL and H₈BINOL Ligands
  • Asymmetric TMSCN Addition to Aldehydes Catalyzed by Binaphthyl Salens

• Asymmetric Hetero-Diels–Alder Reaction

• References

The following sections are included:

• Introduction

• Using Phenyleneethynylene-BINOL Dendrimers for the Recognition of Amino Alcohols

• Using Phenylene-BINOL Dendrimers for the Recognition of Chiral Amino Alcohols
  • Synthesis and Study of Phenylene-BINOL Dendrimers
  • Synthesis of a Phenylene-Binaphthyl Dendrimer with Periphery Hydroxyl Groups

• Using Functionalized BINOLs for the Recognition of Amino Alcohols and Amines

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

• Using Diphenylethylenediamine-BINOL Macrocycles for the Recognition of α-Hydroxycarboxylic Acids
  • Study of the Macrocycles
  • Study of the 6,6'-Substituted Derivatives of the Macrocycles and Their Acyclic Analogs
  • Study of the Macrocyclic Analogs Containing Less Functional Groups

• Using Cyclohexanediamine-BINOL Macrocycles and Their Derivatives for the Recognition of α-Hydroxycarboxylic Acids and Amino Acid Derivatives
  • Synthesis and Characterization of the Binaphthyl Compounds
  • Enantioselective Fluorescent Recognition

• Application of the Cyclohexanediamine-BINOL Macrocycle Sensor in Catalyst Screening

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

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

• References

The following sections are included:

• Chiral Molecular Wires

• A Biphenol Polymer

• Supramolecular Chemistry of Self-Assembly of Racemic and Optically Active Propargylic Alcohols
  • Phenyl- and Pentafluorophenyl-Substituted Propargylic Alcohols
  • Naphthalen-2-yl- and Pentafluorophenyl-Substituted Propargylic Alcohols
  • Naphthalen-1-yl- and Pentafluorophenyl-Substituted Propargylic Alcohols
  • Anthracen-9-yl- and Pentafluorophenyl-Substituted Propargylic Alcohols
  • A Pyridin-2-yl- and Pentafluorophenyl-Substituted Propargylic Alcohol
  • Gel Formation of the Propargylic Alcohols

• References

The following sections are included:

• Index