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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
Title
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