1. Vinyl Epoxides in Organic Synthesis Reporter: Leifeng Wang Supervisor: David Zhigang Wang 2014-06-05 Group Meeting in David’s Group

2. Contents Synthesis of Vinyl Epoxides 1) Strategy A: From Dienes 2) Strategy B: From Epoxy Aldehydes/Ketones 3) Strategy C: From Enone/Enal 4) Strategy D: From Aldehydes Reactions of Vinyl Epoxides 1) Nucleophilic Openings 2) Eliminative Ring-Opening Reactions 3) Rearrangements 4) Radical Reactions 5) Cycloadditions and Formal Cycloadditions Summary Acknowledgment Background 2

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4. Contents Synthesis of Vinyl Epoxides 1) Strategy A: From Dienes 2) Strategy B: From Epoxy Aldehydes/Ketones 3) Strategy C: From Enone/Enal 4) Strategy D: From Aldehydes Reactions of Vinyl Epoxides 1) Nucleophilic Openings 2) Eliminative Ring-Opening Reactions 3) Rearrangements 4) Radical Reactions 5) Cycloadditions and Formal Cycloadditions Summary Acknowledgment Background 4

5. Synthesis of Vinyl Epoxides 5

6. Strategy A: From Dienes Liu, X.; Li, Y.; Wang, G.; Chai, Z.; Wu, Y.; Zhao, G. Tetrahedron: Asymmetry 2006, 17, 750. Alvarez-Manzaneda, E.; Chahboun, R.; Alvarez, E.; Jose Cano, M.; Haidour, A.; Alvarez-Manzaneda, R. n. Org. Lett. 2010, 12, 4450. Jogireddy, R.; Maier, M. E. J. Org. Chem. 2006, 71, 6999. More Electro-Deficient Double Bond More Electro-Rich Double Bond Directed Group 6

7. Strategy B: From Epoxy Aldehydes/Ketones Chandrasekhar, S.; Parida, B. B.; Rambabu, C. J. Org. Chem. 2008, 73, 7826. Jung, M. E.; Berliner, J. A.; Koroniak, L.; Gugiu, B. G.; Watson, A. D. Org. Lett. 2008, 10, 4207. Olefination by Wittig-Type Reactions Olefination by Aldol-Type Condensations 7

8. Strategy C: From Enone/Enal Piccinini, A.; Kavanagh, S. A.; Connon, S. J. Chem. Commun. 2012, 48, 7814. Gadaj, A.; Jonczyk, A. Synthesis 2007, 75. Corey-Chaykovsky Epoxidation Darzen-Type Reactions 8

9. Strategy D: From Aldehydes Davoust, M.; Briere, J.-F.; Metzner, P. Org. Biomol. Chem. 2006, 4, 3048 Kang, B.; Britton, R. Org. Lett. 2007, 9, 5083. Corey-Chaykovsky Epoxidation via Halohydrin-Type Intermediates 9

10. Contents Synthesis of Vinyl Epoxides 1) Strategy A: From Dienes 2) Strategy B: From Epoxy Aldehydes/Ketones 3) Strategy C: From Enone/Enal 4) Strategy D: From Aldehydes Reactions of Vinyl Epoxides 1) Nucleophilic Ring Openings 2) Rearrangements 3) Radical Reactions 4) Cycloadditions and Formal Cycloadditions Summary Acknowledgment Background 10

11. Nucleophilic Ring Openings 11

12. Nucleophilic Ring Openings—Nitrogen Nucleophiles Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gagne,M.R. J. Am. Chem. Soc. 2000, 122, 7905. Lindstrom, U. M.; Olofsson, B.; Somfai, P. Tetrahedron Lett. 1999, 40, 9273. Righi, G.; Manni, L. S.; Bovicelli, P.; Pelagalli, R. Tetrahedron Lett. 2011, 52, 3895. 12

13. Nucleophilic Ring Openings—Nitrogen Nucleophiles Chandrasekhar, S.; Parida, B. B.; Rambabu, C. J. Org. Chem. 2008, 73, 7826. Yaragorla, S.; Muthyala, R. Tetrahedron Lett. 2010, 51, 467. 13

14. Nucleophilic Ring Openings—Oxygen Nucleophiles Gomez, A. M.; Pedregosa, A.; Uriel, C.; Valverde, S.; Lopez, J. C. Eur. J. Org. Chem. 2010, 5619. Buchanan, G. S.; Cole, K. P.; Tang, Y.; Hsung, R. P. J. Org. Chem. 2011, 76, 7027. 14

15. Nucleophilic Ring Openings—Oxygen Nucleophiles Yu, X.-Q.; Hirai, A.; Miyashita, M. Chem. Lett. 2004, 33, 764. Uchida, K.; Yokoshima, S.; Kan, T.; Fukuyama, T. Org. Lett. 2006, 8, 5311. 15

16. Nucleophilic Ring Openings—Oxygen Nucleophiles Nicolaou, K. C.; Nakamura, T. M. B. T. J. Am. Chem. Soc. 2011, 133, 220. Nicolaou, K. C.; Seo, J. H.; Nakamura, T.; Aversa, R. J. J. Am. Chem. Soc. 2011, 133, 214. Fukui, H.; Shiina, I. Org. Lett. 2008, 10, 3153. 16

17. Nucleophilic Ring Openings—Sulfur Nucleophiles Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gagne,M.R. J. Am. Chem. Soc. 2000, 122, 7905. Fedorov, A.; Fu, C.; Linden, A.; Heimgartner, H. Eur. J. Org. Chem. 2005, 1613. 17

18. Nucleophilic Ring Openings—Halide Nucleophiles Hunter, L.; Kirsch, P.; Slawin, A. M. Z.; O’Hagan, D. Angew. Chem. Int. Ed. 2009, 48, 5457. Murakami, T.; Shimizu, T.; Taguchi, K. Tetrahedron 2000, 56, 533. 18

19. Nucleophilic Ring Openings—Halide Nucleophiles Usami, Y.; Ohsugi, M.; Mizuki, K.; Ichikawa, H.; Arimoto, M. Org. Lett. 2009, 11, 2699. Buchanan, G. S.; Cole, K. P.; Tang, Y.; Hsung, R. P. J. Org. Chem. 2011, 76, 7027. 19

20. Nucleophilic Ring Openings—Hydride Nucleophiles Gowrisankar, P.; Pujari, S. A.; Kaliappan, K. P. Chem. Eur. J. 2010, 16, 5858. Ma, K.; Zhang, C.; Liu, M.; Chu, Y.; Zhou, L.; Hu, C.; Ye, D. Tetrahedron Lett. 2010, 51, 1870. 20

21. Nucleophilic Ring Openings—Carbon Nucleophiles Ono, M.; Suzuki, K.; Akita, H. Tetrahedron Lett. 1999, 40, 8223. Myers, A. G.; Siu, M. Tetrahedron 2002, 58, 6397. Lovchik, M. A.; Frater, G.; Goeke, A.; Hug, W. Chem. Biodiversity 2008, 5, 126. Alkenes Friedel-Crafts-Type Reactions Enolate 21

22. Nucleophilic Ring Openings—Carbon Nucleophiles Mahapatra, S.; Carter, R. G. Org. Biomol. Chem. 2009, 7, 4582. Xie, X.; Yue, G.; Tang, S.; Huo, X.; Liang, Q.; She, X.; Pan, X. Org. Lett. 2005, 7, 4057. Di Bussolo, V.; Caselli, M.; Romano, M. R.; Pineschi, M.; Crotti, P. J. Org. Chem. 2004, 69, 8702. 22

23. Rearrangements Boyd, D. R.; Sharma, N. D.; Llamas, N. M.; O’Dowd, C. R.; Allen, C. C. R. Org. Biomol. Chem. 2007, 5, 2267. Deng, X.-M.; Sun, X.-L.; Tang, Y. J. Org. Chem. 2005, 70, 6537 Brichacek, M.; Batory, L. A.; Njardarson, J. T. Angew. Chem., Int. Ed. 2010, 49, 1648. Pericyclic Reactions Meinwald Rearrangements Ring Expansion Rearrangements 23

24. Radical Reactions Ogawa, Y.; Kuroda, K.; Mukaiyama, T. Chem. Lett. 2005, 34, 698. Reactions of Alkoxy Radicals 24

25. Radical Reactions Feldman, K. S.; Fisher, T. E. Tetrahedron 1989, 45, 2969. Yadav, J. S.; Srinivas, D.; Shekharam, T. Tetrahedron Lett. 1994, 35, 3625. Reactions of Carbon Radicals Reactions of Allylic Radicals 25

26. Cycloadditions and Formal Cycloadditions 26

27. Cycloadditions and Formal Cycloadditions Trost, B. M.; Angle, S. R. J. Am. Chem. Soc. 1985, 107, 6123 Yıldırım, M.; Durust, Y. Tetrahedron 2011, 67, 3209. (3 + 2) Cycloadditions 27

28. Cycloadditions and Formal Cycloadditions Pale, P.; Bouquant, J.; Chuche, J.; Carrupt, P. A.; Vogel, P. Tetrahedron 1994, 50, 8035. Liu, L. L.; Chiu, P. Chem. Commun. 2011, 47, 3416 Feng, J.-J.; Zhang, J. J. Am. Chem. Soc. 2011, 133, 7304. (4 + 2) Cycloadditions (4 + 3) Cycloadditions (5 + 2) Cycloadditions 28

29. Summary 29

30. Thank you for your attention! 30

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