1. Catalytic Synthesis of α,β- Unsaturated Carbonyl Derivatives 陈殿峰 2013-11-24 1

2.  Aldol Condensation: Harsh conditions  Olefination Strategy: Costly reagent (Wittig&Wittig-Like) Noxious waste Sensitivity of steric congestion Approaches to α,β-Unsaturated carbonyl derivertives 2

3. 3 Catalytic Synthesis of α,β-Unsaturated carbonyl derivertives

4. Review: Liu, L.-P.; Hammond, G. B. Beilstein. J. Org. Chem. 2011, 7, 606 4 Lewis acid: BF 3 ∙ OEt 2, CuSO 4,Yb(OTf) 3, In(OTf) 3, GaCl 3, FeCl 3, SbF 5 —— Oxophilic Au(I) complex, AgSbF 6, —— Carbophilic Brønsted acid: TfOH, TFA, HBF 4 —— Oxophilic&Carbophilic Alkyne-Carbonyl Metathesis

5. 5 Oxophilic Lewis acid: BF 3 (OEt 2 ), Yb(OTf) 3, In(OTf) 3, GaCl 3, FeCl 3, SbF 5 General Mechanism Li, C.-J. Tetrahedron Letters. 2002, 43, 1613. Alkyne-Carbonyl Metathesis

6. 66 Sisko, J.; Cruuan, D. P. J. Org. Chem, 1992, 57, 4341 BF 3 Et 2 O I. Cikotiene. Org. Lett., 2013, 15, 224

7. 7 U. Jana, J. Org. Chem, 2012, 72, 8780 FeCl 3 R. Huang, Org. Lett. 2006, 8, 231

8. 8 Saito, A.; Hansawa, Y. J. Org. Chem. 2010, 75, 6980 Saito, A.; Hansawa, Y. J. Org. Chem. 2009, 74, 5054 Saito, A.; Hansawa, Y. Org. Lett. 2008, 10, 1783 SbF 5 Cat.-free

9. Yeh, M.-C. Adv. Synth. Catal. 2011, 353, 3290 Saá, C. Org. Lett. 2009, 11, 1531 9 Brønsted Acid

10. Y. Yamamoto, Org. Lett., 2007, 9, 5259 10 Y. Yamamoto, Org. Lett., 2008, 10, 3137 Au(III) complex

11. Liu, L.-P.; K. N. Houk; G. B. Hammond, Angew. Chem. Int. Ed, 2010, 49, 9132 11 Au(I) complex

12. Ag(I) complex M. J. Krische, Org. Lett., 2005, 7, 2493 12 alkyne:aldehyde:AgSbF 6 (1:1:1) or

13. 13 Catalytic Synthesis of α,β-Unsaturated carbonyl derivertives

14. 14 Meyer-Schuster Rearrangement

15. 15 G. B. Dudley, Org. Lett, 2006, 8, 4027 Open air Wet solvent Yoshimatsu, M.; Kataoka, T. J. Org. Chem., 1999, 60, 4798. R 1 = alkyl, R 2 = alkyl, aryl Stoichiomeric activation of alkynes

16. G. B. Dudley, Synlett, 2007, 949; Tetrahedron 2008, 64, 6988 16 Catalyst: Sc(OTf) 3, Cu(OTf) 2, InCl 3, AgOTf Stoichiomeric activation of alkynes

17. Stoichiomeric activation of alcohols metal carbene 17 Zhang, L.-M. Adv. Synth. Catal. 2007, 349, 874 Au(I) complex

18. Au(I or III) complex 18 Zhang, L.-M. J. Am. Chem. Soc. 2006, 128, 8414 Nucleophilic Au III -C(sp2) Zhang, L.-M. Org. Lett. 2006, 8, 4585.

19. Pt(II), Cu(I), Hg(II) Barluenga, J. J. Am. Chem. Soc., 2007, 129, 7772. 19 Nishizawa, M. Org. Lett., 2006, 8, 447.

20. 20 Metal Oxides: General Mechansim: Catalytic activation of substrates

21. 21 VO(acac) 2 West, F. G. J. Am. Chem. Soc. 2009, 131, 7504; J. Org. Chem., 2011, 76, 50 Saucy, G. Synthesis, 1976, 25. Catalytic activation of substrates VO(OSiAr 3 ) 3

22. S. Akai, Org. Lett, 2008, 10, 1867 22 J. A. Osburn, Tetrahedron Letters, 1996, 37, 853 Catalytic activation of substrates

23. Vadari, G. Chem. Eur. J. 2009, 15, 3940 23 Hayashi, Y. Chem. Lett. 1991, 1413-1416 Catalytic activation of substrates

24. T. Yamada, J. Am. Chem. Soc. 2007, 129, 12902 24 Catalytic activation of substrates Summary: Alkyne-Carbonyl Metathesis or Meyer-Schuster Rearrangement ?

25. 25 Beyond Meyer-Schuster  One Pot Reaction:  Tandem reaction:  Cooperative catalysis:

26. M. Lautens, Org. Lett., 2013, 15, 3226. One Pot Reaction: 26 T. D. Sheppard, J. Org. Chem. 2011, 76, 1479

27. Tandem Reaction: Zhang L. M. Angew. Chem. Int. Ed. 2009, 48, 3112. 27 Zhang, L. M. Org. Lett., 2009, 11, 3646.

28. M. J. Gaunt, Angew. Chem. Int. Ed. 2013, 52, 5799. 28 Tandem Reaction:

29. 29 Trost, B. M. J. Am. Chem. Soc. 2001, 123,1230 J. Am. Chem. Soc. 2006, 128,10358 Himo, F. J. Am. Chem. Soc. 2012, 134,19159 Tandem reaction:

30. B. M. Trost, J. Am. Chem. Soc. 2001, 123,12736 Angew. Chem. Int. Ed. 2003, 42, 2063. 30 Tandem Reaction:

31. B. M. Trost, J. Am. Chem. Soc., 2011, 133, 1706 B. M. Trost, J. Am. Chem. Soc., 2011, 133, 12824 B. M. Trost, Nat. Protoc. 2012, 7, 1497. 31 Cooperative catalysis: