Palladium-Catalyzed Arylhalogenation of Alkenes: Seminar Highlights

Seminar conducted by Jian Cao from Jieping Zhu's Lab at EPFL on the topic of Palladium-Catalyzed Arylhalogenation of Alkenes, covering Pd(II)/Pd(IV) and Pd(0)/Pd(II) catalytic cycles, stereochemical studies, historical development, and comprehensive research findings.

• Palladium Catalysis
• Arylhalogenation
• Alkenes
• Seminar
• EPFL

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1. Palladium Palladium- -Catalyzed Catalyzed Arylhalogenation Arylhalogenation of Alkenes of Alkenes Group Seminar Jian Cao (Jieping Zhu s Lab) Laboratory of Synthesis and Natural Products (LSPN) Ecole Polytechnique F d rale de Lausanne (EPFL) 1

2. Outline 1. I 1. Introduction ntroduction 2. 2. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 3. 3. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle 4. 4. Summary and Summary and Outlook Outlook 2

3. Introduction 3

4. Introduction Other types such as radical reactions are not included. 4

5. Outline 1. I 1. Introduction ntroduction 2. 2. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 3. 3. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle 4. 4. Summary and Outlook Summary and Outlook 5

6. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle First arylhalogenation: Heck, R. F. J. Am. Chem. Soc. 1968, 90, 5538. 6

7. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle First arylhalogenation: How was C-Cl bond formed? Heck, R. F. J. Am. Chem. Soc. 1968, 90, 5538. 7

8. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Stereochemical studies: Backvall, J.-E.; Nordberg, R. E. J. Am. Chem. Soc. 1980, 102, 393. 8

9. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Stereochemical studies: Backvall, J.-E.; Nordberg, R. E. J. Am. Chem. Soc. 1980, 102, 393. 9

10. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Sporadic reports between 1980-2008: 10

11. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Comprehensive research: Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 11

12. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 12

13. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Explanation of regioselectivity: Highly reactive PhICl2 leads to 1,2-product; less reactive CuCl2 leads to 1,1-product Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 13

14. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Arylbromination: Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 14

15. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Stereochemistry: Entry Substrate Oxidant Solvent Yield Ratio 49:50 1 cis-48 PhICl2 CuCl2 CuBr2 PhICl2 CuCl2 CuBr2 CH2Cl2 Et2O Et2O CH2Cl2 Et2O Et2O 40% 12:1 2 cis-48 51% >30:1 3 cis-48 41% 5:1 4 trans-48 21% 1:1.6 5 trans-48 45% 1:8 6 trans-48 9% 1:8 Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 15

16. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Stereochemistry: Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 16

17. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Explanation of stereochemistry: Sanford, M. S. et. al. J. Am. Chem. Soc. 2008, 130, 2150; J. Am. Chem. Soc. 2010, 132, 8419. 17

18. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,2-Arylfluorination: Toste, F. D. et. al. J. Am. Chem. Soc. 2014, 136, 4101. 18

19. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle A directing group is necessary: Toste, F. D. et. al. J. Am. Chem. Soc. 2014, 136, 4101. 19

20. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,2-Arylfluorination: Toste, F. D. et. al. J. Am. Chem. Soc. 2014, 136, 4101. 20

21. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle Arylfluorination: Toste, F. D. et. al. J. Am. Chem. Soc. 2014, 136, 4101. 21

22. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,1-Arylfluorination: Toste, F. D. et. al. J. Am. Chem. Soc. 2015, 137, 12207. 22

23. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,1-Arylfluorination: Toste, F. D. et. al. J. Am. Chem. Soc. 2015, 137, 12207. 23

24. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,1-Arylfluorination: Toste, F. D. et. al. Angew. Chem. Int. Ed. 2016, 55, 9045. 24

25. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,1-Arylfluorination: Toste, F. D. et. al. Angew. Chem. Int. Ed. 2016, 55, 9045. 25

26. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,3-Arylfluorination: Toste, F. D. et. al. Chem. Sci. 2017, 8, 2890. 26

27. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,3-Arylfluorination: Toste, F. D. et. al. Chem. Sci. 2017, 8, 2890. 27

28. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 1,3-Arylfluorination: Toste, F. D. et. al. Chem. Sci. 2017, 8, 2890. 28

29. Outline 1. I 1. Introduction ntroduction 2. 2. Pd Pd(II)/ (II)/Pd Pd(IV) Catalytic Cycle (IV) Catalytic Cycle 3. 3. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle 4. 4. Summary and Outlook Summary and Outlook 29

30. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Aryliodination: Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 1778. 30

31. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Bulky phosphine ligands are crucial: Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 1778. 31

32. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Aryliodination: R cannot be H Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 1778. 32

33. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Intermolecular aryliodination: Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 1778. 33

34. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Aryliodination using aryl bromides as substrates: Arylbromination was unsuccessful. Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 14916. 34

35. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Aryliodination using aryl bromides as substrates: Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 14916. 35

36. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Domino reactions: Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 14916. 36

37. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Enantioselective variant: Lautens, M. et. al. J. Am. Chem. Soc. 2011, 133, 14916. 37

38. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Conjunctive carboniodination: Lautens, M. et. al. Angew. Chem. Int. Ed. 2012, 51, 9870. 38

39. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Conjunctive carboniodination: Lautens, M. et. al. Angew. Chem. Int. Ed. 2012, 51, 9870. 39

40. Pd Pd(0)/ (0)/Pd Pd(II) (II) Catalytic Cycle Catalytic Cycle Proposed mechanism: Lautens, M. et. al. Angew. Chem. Int. Ed. 2012, 51, 9870. 40

41. Summary Mechanism Ligands Enantioselective Limitation Arylchlorination Pd(II)/Pd(IV) not required not reported low yield for disubstitued alkenes Arylbromination Pd(II)/Pd(IV) not required not reported low yield for disubstitued alkenes Arylfluorination Pd(II)/Pd(IV) required reported directing groups are required Aryliodination Pd(0)/Pd(II) required reported alkenes impossible for -H elimination End ? 41

42. Thanks for your attention ! 42