studies on synthesis of polycyclic aromatic …polycyclic aromatic hydrocarbons (pahs) 4 pah...

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