studies on synthesis of polycyclic aromatic …polycyclic aromatic hydrocarbons (pahs) 4 pah...
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1
指導教員 市川淳士
ジフルオロカルボカチオンの発生を基盤とする
多環式芳香族炭化水素の合成研究
Studies on Synthesis of Polycyclic Aromatic
Hydrocarbons Based on Difluorocarbocation
Generation
発表者 高尾 豪
2Table of Contents
Chapter 2 Synthesis of PAHs Based on CH3-Arenes via
Domino Cyclization of Difluoroalkenes
Chapter 1 General Introduction
Chapter 3 Synthesis of Substituted Acenes via
Domino or Stepwise Cyclizations from 2-
CF3 Alkenes
Chapter 4 Synthesis of CHF2-Naphthalenes from 1,1-
Difluoroallenes via Pd-Catalyzed Insertion
Chapter 5 Conclusions
3Table of Contents
Chapter 2 Synthesis of PAHs Based on CH3-Arenes via
Domino Cyclization of Difluoroalkenes
Chapter 1 General Introduction
Chapter 3 Synthesis of Substituted Acenes via
Domino or Stepwise Cyclizations from 2-
CF3 Alkenes
Chapter 4 Synthesis of CHF2-Naphthalenes from 1,1-
Difluoroallenes via Pd-Catalyzed Insertion
Chapter 5 Conclusions
4Polycyclic Aromatic Hydrocarbons (PAHs)
5PAH Synthesis: Single Ring Construction
6PAH Synthesis: Multiple Ring Construction
7Plans for PAH Synthesis
8Table of Contents
Chapter 2 Synthesis of PAHs Based on CH3-Arenes via
Domino Cyclization of Difluoroalkenes
Chapter 1 General Introduction
Chapter 3 Synthesis of Substituted Acenes via
Domino or Stepwise Cyclizations from 2-
CF3 Alkenes
Chapter 4 Synthesis of CHF2-Naphthalenes from 1,1-
Difluoroallenes via Pd-Catalyzed Insertion
Chapter 5 Conclusions
9Previous Work: SNV-Type Domino Cyclization
10Previous Work: 1,1-Difluoro-1-alkene Preparation
11Chapter 2: CH3-Arene-Based PAH Synthesis
12CH3-Arene-Based PAH Synthesis
４ Ar1 Ar2 Ar3 Ar4 Ar5
Ar1
Ar2
Ar3
Ar4
Ar5
対称PAH
非対称PAH
５種類 ⇒ 計１５種類
13Introduction of 1st Aryl Groups
1st 2nd
14Preparation of Benzyl Bromides
15Benzylation of CF3-Allyl Silane
16Benzylation of CF3-Allyl Silane
17Preparation of 2-Trifluoromethyl-1-alkenes
18Introduction of 2nd Aryl Groups
1st 2nd
19Preparation of 1,1-Difluoro-1-alkenes (1)
20Preparation of 1,1-Difluoro-1-alkenes (1)
21Generation of Benzyl Lithiums
22Stannylation of Benzyl Bromides
23Preparation of 1,1-Difluoro-1-alkenes (2)
24Domino Cyclization of 1,1-Difluoro-1-alkenes (1)
25Plausible Reaction Mechanism
26Domino Cyclization of 1,1-Difluoro-1-alkenes (2)
27PAH Synthesis by Dehydrogenation
28Summary: Chapter 2
Bull. Chem. Soc. Jpn. 2019, 92, 2019.
29Table of Contents
Chapter 2 Synthesis of PAHs Based on CH3-Arenes via
Domino Cyclization of Difluoroalkenes
Chapter 1 General Introduction
Chapter 3 Synthesis of Substituted Acenes via
Domino or Stepwise Cyclizations from 2-
CF3 Alkenes
Chapter 4 Synthesis of CHF2-Naphthalenes from 1,1-
Difluoroallenes via Pd-Catalyzed Insertion
Chapter 5 Conclusions
30Structures and Properties of Substituted Acenes
31Chapter 3: Synthesis of Substituted Acenes
32Domino Cyclization: SN1’ + SNV-type Reaction
33Domino Cyclization: SN1’ + SNV-type Reaction
34Domino Cyclization and Dehydrogenation
35Stepwise Cyclization
36Stepwise Cyclization
37Stepwise Cyclization
38Stepwise Cyclization
39First Cyclization: SN1’ Reaction
40Second Cyclization: SNV-Type Reaction
41Second Cyclization: SNV-Type Reaction
42Installation of Substituents and Dehydrogenation
43Installation of Substituents and Dehydrogenation
Method A
44Installation of Substituents and Dehydrogenation
Method B
45Oxidative Cation Generation from Difluoroalkenes
46Oxidative Cation Generation from Difluoroalkenes
47Installation of Substituents
48Summary: Chapter 3
49Oxidative Cation Generation from CHF2-Arenes
50Table of Contents
Chapter 2 Synthesis of PAHs Based on CH3-Arenes via
Domino Cyclization of Difluoroalkenes
Chapter 1 General Introduction
Chapter 3 Synthesis of Substituted Acenes via
Domino or Stepwise Cyclizations from 2-
CF3 Alkenes
Chapter 4 Synthesis of CHF2-Naphthalenes from 1,1-
Difluoroallenes via Pd-Catalyzed Insertion
Chapter 5 Conclusions
51Utility of CHF2-Arenes
52Conventional Syntheses of CHF2-Arenes
53Plan for CHF2-Naphthalenes
54Plan for CHF2-Naphthalenes
55Optimization of Conditions: Ligands
56Optimization of Conditions: Ligands
57Optimization of Conditions: Ligands
58Optimization of Conditions: Ligands
59Synthesis of CHF2-Naphthalenes
60Plausible Reaction Mechanism
61Tsuji-Trost Reaction of Difluorinated p-Allyl-Pd
62Summary: Chapter 4
Org. Biomol. Chem. 2019, 17, 5047.
63Conclusion
Bull. Chem. Soc. Jpn. 2019, 92, 2019.
Org. Biomol. Chem. 2019, 17, 5047.
In Preparation
64
65
66Electronic Effects of Fluorine Substituents
67Utility of Fluorine Substituents: Materials
68Utility of Fluorine Substituents: Materials
69Preparation of CH3-Arenes
70Skeletal Rearrangement
71Structure and Properties of Acenes (Linear PAH)
72Pinpoint-Fluorinated Acenes
73Synthesis of Substituted Acenes
74Dehydrogenation
75Screening of Lewis Acids
76Screening of Lewis Acids
77Proposed Mechanism
78Generation of Carbonyl Groups