copper catalyzed aerobic oxidative c-h …kanai/seminar/pdf/lit_y_seki_m1.pdfcontents 2 1....

Copper Catalyzed Aerobic Oxidative

C-H Functionalizations

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

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

1-1. Copper

4

1-2. Oxygen

5

1-3. Cu/O2 system

6

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

2-1. Dimerization of naphthol derivative

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2-1. Dimerization of naphthol derivative

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2-1. Dimerization of naphthol derivative

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2-1. Dimerization of naphthol derivative

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2-1. Dimerization of naphthol derivative

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2-1. Dimerization of naphthol derivative

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2-2. Chlorination and bromination of arene

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2-2. Chlorination and bromination of arene

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2-2. Chlorination and bromination of arene

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2-3. Cyclization of anilides to give oxindole

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2-3. Cyclization of anilides to give oxindole

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2-3. Cyclization of anilides to give oxindole

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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

3-1. Oxidative trifluoromethylation of terminal alkyne

21

3-1. Oxidative trifluoromethylation of terminal alkyne

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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

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

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25

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

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

4-2. Reactivity of Cu(Ⅲ) species

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4-2. Reactivity of Cu(Ⅲ) species

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

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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

5-1. Innovative method of remedy

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5-2. Target residue = Tyrosine

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

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

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

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

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

5-4. Product of tyrosine oxidation

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5-4-1. Proposed mechanism

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5-5. Application to artificial transformation of

Tyr with Cu/O2

40

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

6. Summary

42

Reference

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