発表者

指導教員

高橋一光

市川淳士

Brønsted Acid-Catalyzed

Cationic Cyclizations in Fluoroalcohols

toward Facile Syntheses of

Polycyclic Aromatic Hydrocarbons

含フッ素アルコール溶媒とブレンステッド酸触媒による

カチオン環化を利用した多環式芳香族炭化水素の簡便合成法

Table of Contents

Chapter 1. General Introduction

Chapter 2. Brønsted Acid-Catalyzed Dehydrative Cycloaromatization

of Carbonyl Compounds

Chapter 3. Brønsted Acid-Catalyzed Tandem Cycloaromatization

of Naphthalene-Based Bisacetals

Chapter 4. Brønsted Acid-Catalyzed Intramolecular Hydroarylation

of Unactivated Alkynes

Chapter 5. Conclusion

Polycyclic Aromatic Hydrocarbons (PAHs)

Organic Electronic Devices

Field-Effect Transistor (FET)

Light-Emitting Diode (LED)

Photovoltaic Cell (PV)

General Synthetic Methods for PAHs (1)

◆ Diels-Alder Reaction

General Synthetic Methods for PAHs (2)

◆ Oxidative Photocyclization (Mallory Reaction)

◆ McMurry Coupling

Metal-Catalyzed Syntheses of PAHs

◆ In(III)-Catalyzed Cycloaromatization

◆ Au(I)-Catalyzed Hydroarylation

Brønsted Acid-Catalyzed Syntheses of PAHs

◆ H+-Catalyzed Cycloaromatization

◆ H+-Catalyzed Hydroarylation

Brønsted Acid-Catalyzed Reaction

Fluorinated Alcohols

◆ Acid-Mediated Cationic Cyclization

Survey of This Thesis

Chapter 2, 3

Chapter 4

Table of Contents

Chapter 1. General Introduction

Chapter 2. Brønsted Acid-Catalyzed Dehydrative Cycloaromatization

of Carbonyl Compounds

Chapter 3. Brønsted Acid-Catalyzed Tandem Cycloaromatization

of Naphthalene-Based Bisacetals

Chapter 4. Brønsted Acid-Catalyzed Intramolecular Hydroarylation

of Unactivated Alkynes

Chapter 5. Conclusion

Dehydrative Cycloaromatization

◆ Bradsher Reaction

Bradsher Reaction

Bradsher Reaction

Bradsher Reaction

Preparation of Aldehyde Substrates

◆ Precursors of Phenacenes

◆ Precursors of Acenes

Screening of Conditions

Synthesis of Phenacenes (1)

Synthesis of Phenacenes (2)

◆ [4]Phenacene

◆ [4]Helicene

Synthesis of Triphenylenes

Synthesis of Triphenylenes

Synthesis of Triphenylenes

Synthesis of Triphenylenes

◆ Preparation

Synthesis of Acenes (1)

Synthesis of Acenes (2)

◆ Tetraphene

◆ Tetracene

Cycloaromatization of Vinyl Ether & Acetal

◆ Vinyl Ether

◆ Acetal (1,3-Dioxolane)

Table of Contents

Chapter 1. General Introduction

Chapter 2. Brønsted Acid-Catalyzed Dehydrative Cycloaromatization

of Carbonyl Compounds

Chapter 3. Brønsted Acid-Catalyzed Tandem Cycloaromatization

of Naphthalene-Based Bisacetals

Chapter 4. Brønsted Acid-Catalyzed Intramolecular Hydroarylation

of Unactivated Alkynes

Chapter 5. Conclusion

Ortho-Fused Benzenoids (1)

Ortho-Fused Benzenoids (2)

Synthesis of Six-Hexagon Benzenoids

Screening of Conditions (1)

Screening of Conditions (2)

Synthesis of Six-Hexagon Benzenoids (1)

◆ Symmetrical Substrates

Synthesis of Six-Hexagon Benzenoids (2)

◆ Unsymmetrical Substrates

Preparation of Precursors

Table of Contents

Chapter 1. General Introduction

Chapter 2. Brønsted Acid-Catalyzed Dehydrative Cycloaromatization

of Carbonyl Compounds

Chapter 3. Brønsted Acid-Catalyzed Tandem Cycloaromatization

of Naphthalene-Based Bisacetals

Chapter 4. Brønsted Acid-Catalyzed Intramolecular Hydroarylation

of Unactivated Alkynes

Chapter 5. Conclusion

Transition Metal-Catalyzed Hydroarylation

Brønsted Acid-Mediated Hydroarylation

Hydroarylation of Unactivated Alkynes

Screening of Conditions (1)

Hypothesis for Improvement of Yields

◆ Proposed Side Reaction

Hypothesis for Improvement of Yields

◆ Suppressing Side Reaction

Screening of Conditions (2)

Synthesis of Phenacenes

Two-Phase Solvent System (1)

Two-Phase Solvent System (2)

◆ Proposed Mechanism

Recycling HFIP Solution of TsOH

Conclusion

Application of PAHs

◆ Mobility of PAHs

Other Synthetic Method for PAHs

◆ Aldol Condensation

Property of HFIP (1)

◆ Ionizing Power

N = log (k / k0 ) k0 : 80% EtOH / H2O溶媒中における加溶媒分解の速度定数

k0 : 測定溶媒中における加溶媒分解の速度定数

Property of HFIP (2)

◆ Nucleophilicity

N = log (k / k0 ) k0 : 80% EtOH / H2O溶媒中における加溶媒分解の速度定数

k0 : 測定溶媒中における加溶媒分解の速度定数

Property of HFIP (3)

◆ Hydrogen Bonding Donor

◆ Hydrogen Bonding-Enhanced Brønsted Acid

Preparation of Precursors of Phenacenes

◆ a-Me Substituted Substrate

◆ Ketone

Preparation of Precursors of Acenes

◆ Ketone

◆ Acetal (1,3-Dioxorane)

Screening of Conditions (2)

SEAr of Naphthalene

◆ Bromination

◆ Friedel-Crafts type Cyclization

Cationic Cyclization of CF3-Substituted Substrate

◆ Value of sm

◆Cationic Cyclization of Vinylether

Preparation of Bisacetals (1)

◆ Preparation of Boronic Ester

Preparation of Bisacetals (2)

Selectivity in Tandem Cycloaromatization (1)

◆ 2,7-Substitution

Selectivity in Tandem Cycloaromatization (2)

◆ 2,7-Substitution

Selective Tandem Cycloaromatization (1)

◆ 1,6-Substitution

Selective Tandem Cycloaromatization (2)

◆ 1,6-Substitution

Selective Tandem Cycloaromatization (3)

◆ 1,7-Substitution

Selective Tandem Cycloaromatization (4)

◆ 1,7-Substitution

Hydroarylation of Unactivated Alkynes

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