N-Heterocyclic Carbenes: A Continuum of Progress

Transcription

1 N-Heterocyclic Carbenes: A Continuum of Progress or just another case of: how nature influences our daily chemistry life Reviews: J. Izquierdo, G.E. Hudson, D.T. Cohen, K.A. Scheidt, Angew. Chem. Int. Ed. 2012, 51, C.E.I. Knappke, A. Imami, A. Jacobi von Wangelin, ChemCatChem 2012, 4, X. Bugaut, F. Glorius, Chem. Soc. Rev. 2012, 41, W.A. Herrmann, C. Köcher, Angen. Chem. Int. Ed. Engi. 1997,36, N. Marion, S. Dez-Gonzlez, S.P. Nolan, Angew. Chem. Int. Ed. 2007, 46, Jana Franke slide 1

2 Content Introduction Reactivity, Modes of Action, Thiamine, Arduengo Carbene, Breslow intermediate Umpolung Benzoin condensation Stetter reaction Homoenolates Activation Aroylation reaction Redox reaction/oxidation Diels Alder reaction 2

3 Reactivity electronrich, aromatic or unsaturated heterocycles, stable carbene pka: strong bases counterion have no significant effect NHC resonance stabilization [1 basicity vs. nucleophilicity: NHC are highly nucleophilic [1] [2] R.W. Alder, P.R. Allen, S.J. Williams, J. Chem. Soc., Chem. Commun. 1995, [3] T. L. Amyes, S.T. Diver, J.P. Richard, F.M. Rivas, K. Toth, J. Am. Chem. Soc. 2004, 126, [4] a) M.W. Washabaugh, W.P. Jencks, J. Am. Chem Soc. 1989, 111, ; b) Y. Chu, H. Deng, J.-P. Cheng, J. Org. Chem. 2007, 72, ; c) F.G. Bordwell, A.V. Satish, J. Am. Chem. Soc. 1991, 113, ; d) A.M. Magill, K.J. Cavell, B.F. Yates, J. Am. Chem. Soc. 2004, 126,

4 N-Heterocyclic Carbenes: modes of action [5] F. Glorius, K. Hirano, ernst Schering Foundation Symposium Proceedings 2009,

5 Wanzlick equilibrium thermolysis experiment of Wanzlick: equilibrium between the dimer and the free carbene 1999, Lemal et al. could observe the Wanzlick equilibrium of dibenzotetrafulvalene derivatives and their carbenes [6] a) H.W. Wanzlick, H.J. Schönherr, Angew. Chem. Int. Ed. Engl. 1968, 7, ; b) P. Luger, G. Ruban, Acta Crystallogr. Sect. B 1971, 27, [7] K. Öfele, J. Organomet. Chem. 1968, 12, P42-P43. [8] V.P.W. Böhm, W.A. Herrmann, Angew. Chem. Int. Ed. 2000, 39, [9] Y. Liu, P.E. Lindner, D.M. Lemal, J. Am. Chem. Soc. 1999, 121,

6 Arduengo carbene 1991, first synthesis and isolation of a stable diaminocarbene by Arduengo tricyclohexyl phosphine ligands: e - -rich increased metathesis activity NHC ligand: strong s-donor and poor p-acceptor; stabilization of 14 e -Ru-intermediate in catalytic cycle more effective catalyst [10] A.J. Arduengo III, R.L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113,

7 Thiamine: a natural carbene Food sources [12] thiamine pyrophosphate (TPP); coenzyme in catabolism of sugars and amino acids synthesized in bacteria, fungi and plants essential nutrient for animals and mammals [11] M. Pohl, G.A. Sprenger, M. Müller, Current Opinion in Biotechnology 2004, 15, [12] 7

8 Coenzyme thiamine pyruvic acid decarboxylation: acetoin synthesis: [13] P. Delos Boyer, D.S. Sigman, The Enzymes: Mechanism of Catalysis 1992, 3 rd Edition, Academic Press. 8

9 Breslow intermediate Jeffrey W. Bode (ETH Zurich): The Breslow intermediate is the Higgs boson of the N-heterocyclic carbene catalysis field. Chemical & Engeneering News 2012, 90, p. 8 Breslow recognized similarities in reactivity of thiamine and cyanide in benzoin condensation stabilized carbene [14] R. Breslow, J. Am. Chem. Soc. 1958, 80, [15] A. Berkessel, S. Elfert, V. R. Yatham, J.M. Neudörfl, N.E. Schlörer, J.H. Teles, Angew. Chem. Int. Ed. 2012, early view. 9

10 Benzoin condensation: Cassialoin isolated from the plant extracts of Cassia garrettiana Cassia garrettiana [19] in vivo studies: inhibits tumor growth and metastasis in mice 2007, Suzuki et al. reported first stereoselective total synthesis [16] K. Hata, M. Kozawa, K. Baba, Chem. Pharm. Bull. 1976, 24, [17] Y. Kimura, M. Sumiyoshi, M. Taniguchi, K. Baba, Cancer Sci. 2008, 99, [18] Y. Koyama, R. Yamaguchi, K. Suzuki, Angew. Chem. Int. Ed. 2008, 47, [19] 10

11 Stetter reaction: (±)-hirsutic acid C isolated from stereum hirsutum Stereum hirsutum [19] members of this family exhibit antibiotic and antitumor reactivity tricyclic sesquiterpene 1979, first stereocontrolled total synthesis by Trost et al. [20] B.M. Trost, C.D. Shuey, F. Dininno, S.S. Mcelvain, J. Am. Chem. Soc. 1979, 101, [21] a) F.W. Comer, J. Trotter, J. Chem. Soc. B. 1966, 11-18; b) F.W. Comer, F. Mccapra, I.H. Qureshi, A.I. Scott, Tetrahedron 1967, 23, ; c) T.C. Feline, G. Mellows, R.B. Jones, L. Phillips, J. Chem. Soc. Chem. Commun. 1974, [19] 11

12 Homoenolates reaction mechanism: 2004, Glorius and Bode independently reported the synthesis of g-butyrolactones by homoenolate annulation of aldehydes [22] C. Burstein, F. Glorius, Angew. Chem. Int. Ed. 2004, 43, [23] S.S. Sohn, E.L. Rosen, J.W. Bode, J. Am. Chem. Soc. 2004, 128, slide 12

13 Homoenolates: (-)-bakkenolide S 1968, first isolation of bakkane sequiterpene containing a cisfused 5,6-bicyclic core show antifeedant effects; inhibit platelet aggregation; anticancer activity against a variety of tumor cell lines [24] N. Abe, R. Onoda, K. Shirahat, T. Kato, M.C. Woods, Y. Kitahara, Tetrahedron Lett. 1968, [25] a) L.F. Silva, Synthesis 2001, ; b) T.J. Brocksom, U. Brocksom, M.G. Constantino, Quim. Nova 2008, 31, [26] a) G.R. Jamieson, E.H. Reid, B.P. Turner, A.T. Jamieson, Phytochemistry 1976, 15, ; a) K. Kano, K. Hayashi, H. Mitsuhashi, Chem. Pharm. Bull. 1982, 30, [27] E.N. Phillips, J.M. Roberts, K.A. Scheidt, Org. Lett. 2010, 12, slide 13

14 What else is possible besides Umpolung reactions? NHCs have been studied for their ability to promote primarily the benzoin condensation. lately, dramatic progress in understanding their intrinsic properties and in their synthesis have made them available to organic chemists [28] N. Marion, S. Dez-Gonzlez, S.P. Nolan, Angew. Chem. Int. Ed. 2007, 46, [29] E.M. Phillips, A. Chan, K.A. Scheidt, Aldrichimica Acta. 2009, 42,

15 Aroylation reactions: atroviridin isolated from Garcinia atroviridus, oxygenated xanthone reaction mechanism: [30] J. Kosin, N. Ruangrungsi, C. Ito, H. Furukawa, Phytochemistry 1998, 47, [31] Y. Suzuki, Y. Fukuta, S. Ota, M. Kamiya, M. Sato, J. Org. Chem. 2011, 76,

16 Redox reactions and Oxidations path A: oxidation formation of electrophilic acyl azolium ion via two electron transfer path B: oxygenation oxygen atom transfer from oxidant [32] C.E.I. Knappke, A. Imami, A. Jacobi von Wangelin, ChemCatChem 2012, 4,

17 Oxidative macrolactonization: (+)-dactylolide Isolated from Vanuatu sponge Dactylospongia sp. Dactylospongia sp. [35] cytotoxic; inhibitory activites towards tumor cell growth in leukemia and ovarian cancer [33] A. Cutignano, I. Bruno, G. Bifulco, A. Casapullo, C. Debitus, L. Gomez-Paloma, R. Riccio, Eur. J. Org. Chem. 2001, [34] K. Lee, H. Kim, J. Hong, Angew. Chem. Int. Ed. 2012, 51, [35] 17

18 Diels Alder proposed process: enolate precursors: [36] X. Zhao, K.E. Ruhl, T. Rovis, Angew. Chem. Int. Ed. 2012, early view 18

19 Hetero Diels Alder reactions catalyst: oxidants: [36] X. Zhao, K.E. Ruhl, T. Rovis, Angew. Chem. Int. Ed. 2012, early view. 19

20 Summary & additional information summary of this talk Reactivity: Arduengo Carbene, Breslow Intermediate, Thiamine present research and additional information Reactions: Umpolung Benzoin condensation, Stetter reaction, Homoenolates Aroylation Redox reactions/ Oxidations Diels Alders 20

21 Summary & additional information summary of this talk present research and additional information NHC as ligands for metal complexes: W. A. Herrmann, Angew. Chem. Int. Ed. 2002, 41, b-borylation: C-B bond formation K.-S. Lee, A.R. Zhugralin, A.H. Hoveyda, J. Am. Chem. Soc. 2009, 131, rearrangement/quarternary stereocenters: K. Hirano, A.T. Biju, I. Piel, F. Glorius, J. Am. Chem. Soc. 2009, 131, ; M. Padmanaban, A.T. Biju, F. Glorius, J. Am. Chem. Soc. 2011, 13, NHC research: Vijay Nair, Tom Rovis, Steven P. Nolan, Wolfgang A Herrmann [37] [38] [39] [40] Jeffrey W. Bode [37], Frank Glorius [38], Karl A. Scheidt [39], A. Jacobi von Wangelin [40] 21

22 Thank you for your attention slide 22