Copper Catalyzed Aerobic Oxidative
C-H Functionalizations

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary

2

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary31-1. Copper41-2. Oxygen51-3. Cu/O2 system

6

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary7

2-1. Dimerization of naphthol derivative8

2-1. Dimerization of naphthol derivative9

2-1. Dimerization of naphthol derivative10

2-1. Dimerization of naphthol derivative11

2-1. Dimerization of naphthol derivative12

2-1. Dimerization of naphthol derivative13

2-2. Chlorination and bromination of arene142-2. Chlorination and bromination of arene15

2-2. Chlorination and bromination of arene162-3. Cyclization of anilides to give oxindole17

2-3. Cyclization of anilides to give oxindole18

2-3. Cyclization of anilides to give oxindole

19

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary20

3-1. Oxidative trifluoromethylation of terminal alkyne

21

3-1. Oxidative trifluoromethylation of terminal alkyne

22

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary23

4-1. Mechanism of formation of Cu(Ⅲ) species244-1. Mechanism of formation of Cu(Ⅲ) species254-1. Mechanism of formation of Cu(Ⅲ) species

264-2. Reactivity of Cu(Ⅲ) species274-2. Reactivity of Cu(Ⅲ) species284-2. Mechanism of Reaction of Cu(Ⅲ) species

29

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary30

5-1. Innovative method of remedy

315-2. Target residue = Tyrosine

325-3. Tyrosyl radical ～Alzheimer‘s disease～33

5-3. Tyrosyl radical ～Alzheimer‘s disease～34

5-3. Tyrosyl radical ～Alzheimer‘s disease～35

5-3. Tyrosyl radical ～Alzheimer‘s disease～36

5-3. Tyrosyl radical ～Alzheimer‘s disease～37

5-4. Product of tyrosine oxidation38

5-4-1. Proposed mechanism39

5-5. Application to artificial transformation ofTyr with Cu/O240

Contents
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 toC-H oxidation reactions

5. Application to artificial transformation of amino acid6. Summary41

6. Summary42

Reference43