1. Catalytic Heterocycle Synthesis Group http://www.chs.dicp.ac.cn/ 万伯顺 bswan@dicp.ac.cn 杂环合成中的 环加成与环化反应

2. Why Cycloadditon? Advantages:  Two C-C bonds & One C-N bond simultaneously  High atom efficiency Problems:  Regioselectivity  Chemoselectivity D. Siegel et al, J. Am. Chem. Soc. 2010, 132, 5924.

3. Why Iron? Iron (0.02 US$/mol) US$ per mol 2011 Iron(0) complex Organometallics, 1996, 15, 2713 Organometallics, 2002, 21, 2578 Iron(I) complex Wan

4. Iron Catalytic System

5. Holland’s investigation : The binding affinity toward the low-valent iron: Holland, P. L. et al. Inorg. Chem. 2006, 45, 5742. Problems and Solutions

7. EntryIron saltLigandFe%Conv.(%)3a% 1FeCl 3 -20%00 2FeCl 3 dppe20%9997 3FeCl 3 dppp20%10097 4FeBr 3 dppp20%9989 5FeBr 2 dppp20%10099 6FeI 2 dppp20%100>99 7FeCl 3 dppp10%169 8FeBr 2 dppp10%7568 9FeI 2 dppp10%100>99 10FeI 2 dppp5%10099 11FeI 2 dppp2.5%136

8. Cycloaddition of Diynes and Unactivated Nitriles

9. (Continued) Cycloaddition of Tetrayne

10. All-intramolecular Cycloaddition Cycloaddition of Alkynenitrile and Alkyne

11. Control Experiments

12. Possible Pathways to Form Pyridines With Wang, C. X. Angew. Chem. Int. Ed. 2011, 50, 7162

13. a 5 mol% catalyst, 5 equiv nitrile b 10 mol% catalyst, 2 equiv nitrile With Wang, C. X. J. Org. Chem. 2013, 78, 3065

14. [2+2+2] Cycloaddition in Pure Water

15. With Xu, F. ChemSusChem. 2012, 5, 854 [2+2+2] Cycloaddition in Pure Water

16. [2+2+2] Cycloaddition New Cycloaddition of Oximes and Diynes Aldehyde [Ru] Oxime Catalyst H2OH2O

17.  Reactivity of the C=N double bond  Water generated from cycloadducts  Rearrangement of oximes into amides New Cycloaddition of Oximes and Diynes

19. Key Point With Xu, F. Chem Eur J 2013, 19, 2252.

20. Nickel-catalyzed [3 + 2] cycloaddition of diynes with MAs Chem. Commun. 2013, ASAP C3CC41061G C-C bond cleavage N-C bond cleavage

21. Proposed mechanism

22. Building blocks What ? Synthesis of Pyrroles via Cyclization 杂原子 叁键 双键 电子 / 空间 调控基团

23. × × DMF, Ar 140 o C Synthesis of Pyrroles via Cyclization Ts = p-CH 3 PhSO 2 -

24. Synthesis of Pyrroles via Cyclization With Xin, X. Y. Angew. Chem. Int. Ed. 2012, 51, 1693.

25. "α" Migration Mechanism Study

26. "β" Migration Mechanism Study

27. Crossover Experiment

28. Competition Experiment

29.  Cyclization of Aza-enynes EntryCatalystSolvent3a(%) 1-DMF-85 2BPO (20)DMF1526 3AIBN (20)DMF2943 4NHPI (20)DMF4231 5TEMPO (20)DMF-66 6Anthraquinone (20)DMF-93 7DDQ (20)DMF84- 8DDQ (20)CCl 4 80- 9DDQ (20)Benzene85- 11DDQ (10)THF89- 12DDQ (10)THF92- Catalyst + 2a(%) J. Org. Chem. 2013 ASAP jo400387b

30. EntryCatalystSolventTime(h)2a% 1DDQ-H 2 THF4897 2HydroquinoneTHF4895 3PhenolTHF4874 4H2OH2OTHF4887 5MeOH (50)THF4893 6MeOH (solvent)MeOH4897  Cyclization of Aza-enynes J. Org. Chem. 2013 ASAP jo400387b

32. Mechanism Study

33. Proposed Mechanism J. Org. Chem. 2013 ASAP jo400387b

34. With Yu, X. Z. J. Org. Chem. 2013, jo4004635 Another example of cyclization with Ts migration

35. Xingwei Li,* Boshun Wan*, Angew. Chem. Int. Ed. 2013, 52, 2577 Other important finding

36. 环加成与环化反应小结 六元环 : (1) JOC jo400387b (2) Unpublished results 五元环 : ACIE, 2012, 51, 1693 四元环 : Unpublished results 三元环 : Unpublished results