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Copper Catalyzed Aerobic Oxidative C-H Functionalizations

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Page 1: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Copper Catalyzed Aerobic Oxidative

C-H Functionalizations

Page 2: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

2

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 3: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

3

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 4: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

1-1. Copper

4

Page 5: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

1-2. Oxygen

5

Page 6: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

1-3. Cu/O2 system

6

Page 7: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

7

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 8: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-1. Dimerization of naphthol derivative

8

Page 9: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-1. Dimerization of naphthol derivative

9

Page 10: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-1. Dimerization of naphthol derivative

10

Page 11: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-1. Dimerization of naphthol derivative

11

Page 12: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-1. Dimerization of naphthol derivative

12

Page 13: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-1. Dimerization of naphthol derivative

13

Page 14: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-2. Chlorination and bromination of arene

14

Page 15: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-2. Chlorination and bromination of arene

15

Page 16: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-2. Chlorination and bromination of arene

16

Page 17: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-3. Cyclization of anilides to give oxindole

17

Page 18: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-3. Cyclization of anilides to give oxindole

18

Page 19: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

2-3. Cyclization of anilides to give oxindole

19

Page 20: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

20

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 21: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

3-1. Oxidative trifluoromethylation of terminal alkyne

21

Page 22: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

3-1. Oxidative trifluoromethylation of terminal alkyne

22

Page 23: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

23

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 24: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

4-1. Mechanism of formation of Cu(Ⅲ) species

24

Page 25: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

25

4-1. Mechanism of formation of Cu(Ⅲ) species

Page 26: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

26

4-1. Mechanism of formation of Cu(Ⅲ) species

Page 27: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

4-2. Reactivity of Cu(Ⅲ) species

27

Page 28: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

4-2. Reactivity of Cu(Ⅲ) species

28

Page 29: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

4-2. Mechanism of Reaction of Cu(Ⅲ) species

29

Page 30: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

30

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 31: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

5-1. Innovative method of remedy

31

Page 32: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

5-2. Target residue = Tyrosine

32

Page 33: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

5-3. Tyrosyl radical ~Alzheimer‘s disease~

33

Page 34: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

34

5-3. Tyrosyl radical ~Alzheimer‘s disease~

Page 35: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

35

5-3. Tyrosyl radical ~Alzheimer‘s disease~

Page 36: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

36

5-3. Tyrosyl radical ~Alzheimer‘s disease~

Page 37: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

37

5-3. Tyrosyl radical ~Alzheimer‘s disease~

Page 38: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

5-4. Product of tyrosine oxidation

38

Page 39: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

5-4-1. Proposed mechanism

39

Page 40: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

5-5. Application to artificial transformation of

Tyr with Cu/O2

40

Page 41: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Contents

41

1. Introduction

2. C-H oxidation initiated by single-electron transfer

3. C-H oxidation that resemble organometallic reaction

4. Organometallic copper (Ⅲ) chemistry relevant to C-H oxidation reactions

5. Application to artificial transformation of amino acid 6. Summary

Page 42: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

6. Summary

42

Page 43: Copper Catalyzed Aerobic Oxidative C-H …kanai/seminar/pdf/Lit_Y_Seki_M1.pdfContents 2 1. Introduction 2. C-H oxidation initiated by single-electron transfer 3. C-H oxidation that

Reference

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