1. Reactions Involve Sulfur Ylides 陈殿峰 2012.05.12 陈殿峰 2012.05.12

2. 22 1. Introduction 2. Corey-Chaykovsky Reaction 3. Cyclization 4. Tandem Reaction 5. Conclusion 2 Contents

3. 33 1.Introduction 3 Reference: Dai, L-X; Aggarwal, V. K. Chem. Rev. 1997, 97, 2341 Aggarwal, V. K. Acc. Chem. Res. 2004, 37, 611 Aggarwal, V. K. Chem. Rev. 2007, 107, 5841 Commonly used for methylene transfer R 1 ≠ R 2 ≠ Me : chiral sulfur ylide More versatile

4. 44 2.1 Epoxidation 4 Method 1: Method 2: 2. Corey-Chaykovsky Reaction

5. 55 Limitation: 1. Aryl aldehyde only 2.Strong nuclephility of sulfide only 3. High active halides only 2.1 Epoxidation 2. Corey-Chaykovsky Reaction

6. 666 Aggarwal, V. K. J. Am. Chem. Soc. 1994, 116, 5973-5974. Aggarwal, V. K. J. Am. Chem. Soc. 1996, 118, 7004-7005. Slow addition for 24h 2.1 Epoxidation 2. Corey-Chaykovsky Reaction

7. 777 Aggarwal, V. K. J. Am. Chem. Soc. 1994, 116, 5973-5974. Mechanism: 2.1 Epoxidation 2. Corey-Chaykovsky Reaction

8. 88 First example 8 L-X, Dai. J. Chem. Soc., Perkin Trans. 1996, 867 2.2 Aziridination 2. Corey-Chaykovsky Reaction

9. 99 First Asymmetric example 9 2.2 Aziridination 2. Corey-Chaykovsky Reaction Saito, T. Tetrahedron Lett. 2001, 42, 5451

10. 10 Aggarwal, V. K. J. Chem. Soc., Perkin Trans. 2001, 1635 2.2 Aziridination 2. Corey-Chaykovsky Reaction

11. 11 Aggarwal, V. K. Angew. Chem. Int. Ed. 2001, 40, 1433 2.2 Aziridination 2. Corey-Chaykovsky Reaction

12. 12 When using stoichiometric sulfonium salts: Yield up to 99% d.r. Up to >99:1 Ee up to 99% Yong, Tang. J. Am. Chem. Soc. 2006, 128, 9730-9740. 2. Corey-Chaykovsky Reaction 2.3 Cyclopropanation

13. 13 Aggarwal, V. K. J. Chem. Soc., Perkin Trans. 2000, 3267 Aggarwal, V. K. Chem. Eur. J. 2006, 12, 568 2. Corey-Chaykovsky Reaction 2.3 Cyclopropanation

14. 14 Aggarwal, V. K. J. Chem. Soc., Perkin Trans. 2000, 3267 Aggarwal, V. K. Angew. Chem. Int. Ed. 2001, 40, 1433 2. Corey-Chaykovsky Reaction 2.3 Cyclopropanation

15. 15 2. Corey-Chaykovsky Reaction 2.3 Cyclopropanation MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 3240-3241. W-J, Xiao. J. Org. Chem. 2011, 76, 281-284

16. 16 Doerring, W. v.; Schreiber, K. J. Am. Chem. Soc. 1955, 77, 514-520 Jimenez, L. S. J. Am. Chem. Soc. 1994, 116, 4977-4978 16 3. Cyclization 3.1 Vinylsulfur ylide

17. 17 Aggarwal, V. K. Angew. Chem. Int. Ed. 2006, 45, 7066-7069 3. Cyclization 3.1 Vinylsulfur ylide

18. 18 Aggarwal, V. K. Org. Lett. 2009, 11, 257-260 Proposed Mechanism: 3. Cyclization 3.1 Vinylsulfur ylide

19. 19 W-J, Xiao. Chem. Commun. 2011, 47, 1869-1871 3. Cyclization 3.1 Vinylsulfur ylide

20. 20 Aggarwal, V. K. Org. Lett. 2011, 13, 3060-3063 Proposed Mechanism: 3. Cyclization 3.1 Vinylsulfur ylide

21. 21 Yong Tang. J. Org. Chem. 2008, 73, 6909-6912 Danheiser, R. L. J. Am. Chem. Soc. 1998, 120, 9690-9691 3. Cyclization 3.2 Fomal 4+1

22. 22 Wen-Jing Xiao. Angew. Chem. Int. Ed. 2010, 49, 4495-4498 Yong Tang. Tetrahedron. 2008, 64, 5583-5589 Gaunt. M. J. Chem Rev. 2007, 107, 5596-5605 3. Cyclization 3.2 Fomal 4+1

23. 23 Proposed Mechanism: Bolm, C. J. Am. Chem. Soc. 2012, 134, 6924-6927 3. Cyclization 3.2 Fomal 4+1

24. 24 Yong Tang. J. Am. Chem. Soc. 2008, 130, 5408-5409 Yong Tang. J. Org. Chem. 2010, 75, 3454-3457 Proposed Mechanism: 4. Tandem Reactions

25. 25 Junliang Zhang. Chem. Asian. J. 2009, 4, 1527-1529 Proposed Mechanism: 4. Tandem Reactions

26. 26 Proposed Mechanism: Wen-Jing Xiao. Angew. Chem. Int. Ed. 2009, 48, 9542-9545 W-J, Xaio. J. Org. Chem. 2012, 77, 1072-1080. 4. Tandem Reactions

27. 27 W-J, Xiao. J. Am. Chem. Soc. 2008, 130, 6946-6948. W-J, Xiao. Chem. Eur. J. 2012, 18, 4073-4079. Proposed Mechanism: 4. Tandem Reactions

28. 28 Kouichi Ohe; Sakae Uemura. Org. Lett. 2003, 5, 2619-2621 Proposed Mechanism: 4. Tandem Reactions

29. 29 Skrydstrup, T. Angew. Chem. Int. Ed. 2012, 51, 1-5 Proposed Mechanism: 4. Tandem Reactions

30. 30 5. Conclusion Y-C, Chen. J. Am. Chem. Soc. 2008, 130, 2456-2457 Nitrogen Phophorus: Gaunt, M. J. Angew. Chem. Int. Ed. 2004, 43, 4641-4644 1). Sulfur ylides are important synthon in organic synthesis; 2). New type ylide with unconventional properties need to be developed; 3). Sulfide/metal-carbenoid system could be used in more kinds of reactions; 4). Asymmetric proceeds using unchiral sulfide are potentially prospective. Other Ylides:

31. 31