Reactions Involve Sulfur Ylides 陈殿峰 陈殿峰

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

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

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

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

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

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

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

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

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

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

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, Corey-Chaykovsky Reaction 2.3 Cyclopropanation

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

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

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

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

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

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

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

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

21 Yong Tang. J. Org. Chem. 2008, 73, Danheiser, R. L. J. Am. Chem. Soc. 1998, 120, Cyclization 3.2 Fomal 4+1

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

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

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

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

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

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

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

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

30 5. Conclusion Y-C, Chen. J. Am. Chem. Soc. 2008, 130, Nitrogen Phophorus: Gaunt, M. J. Angew. Chem. Int. Ed. 2004, 43, ). 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:

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