1

2

2. Hydrogen Atom Transfer (HAT) Reactions

3

3. Challenges of Hydrogen Atom Transfer

4. Contents

4

5. Proton-Coupled Electron Transfer (PCET)

5

6

6. Thermochemistry of PCET

7

7. PCET in Photosystem II

8. Asst. Prof. Robert R. Knowles

8

9. Contents

9

10. Reductive PCET for Ketyl Generation

10

11. Optimization of Reaction Conditions

11

12. Ketyl-Olefin Coupling -Substrate Scope-

12

13. Luminescence Quenching Studies

13

14. Proposed Catalytic Cycle

14

15. Contents

15

16. Oxidative PCET for Amidyl Generation

16

17. Optimization of Reaction Conditions

17

18. Carboamidation -Substrate Scope-

18

19. Proposed Catalytic Cycle

19

20. Task for Catalytic Hydroamidation

20

21. Screening of H-atom Donor

21

22. Hydroamidation –Substrate Scope-

22

23. Luminescence Quenching Studies

23

24. Competition-Qenching Studies

24

25. Computational Evaluation of Hydrogen Bonding

25

26. Contents

26

27. Intramolecular PCET

27

28. Design of Ring-Opening Reaction

28

29. Optimization Reaction Conditions

29

30. Ring-Opening Reaction –Substrate Scope-

30

31. Effect of Remote PMP Group

31

32. Effect of Proximal Aryl Group

32

33. Summary

33

34

Appendix

35

Redox Potential and pKa

Asymmetric Aza-Pinacol Cyclization

36

Halogenation Reactions

37

Intramolecular ET Strategy

38

39

H-Bonding Promoted HAT

40

Reaction Rate of Radical Cyclization

41

Kinetics of PCET (Marcus Theory)

42

Crystal Structure of OEC