Catalytic Synthesis of α,β- Unsaturated Carbonyl Derivatives 陈殿峰

 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 Catalytic Synthesis of α,β-Unsaturated carbonyl derivertives

Review: Liu, L.-P.; Hammond, G. B. Beilstein. J. Org. Chem. 2011, 7, 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 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, Alkyne-Carbonyl Metathesis

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

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

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

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

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

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

13 Catalytic Synthesis of α,β-Unsaturated carbonyl derivertives

14 Meyer-Schuster Rearrangement

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

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

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

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.

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

20 Metal Oxides: General Mechansim: Catalytic activation of substrates

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

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

Vadari, G. Chem. Eur. J. 2009, 15, Hayashi, Y. Chem. Lett. 1991, Catalytic activation of substrates

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

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

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

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

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

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:

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

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