The Role Of Ionic Liquids In Co-catalysis Of Baylis-hillman Reaction: Interception Of Supramolecular Species Via Electrospray Ionization Mass Spectrometry

The Baylis-Hillman reaction is a general and multifaceted method for C - C bond formation in organic synthesis. Using electrospray ionization mass spectrometry in both the positive and negative ion modes, we performed on-line monitoring of the reaction in the presence of imidazolium ionic liquids. Loosely bonded supramolecular species formed by coordination of neutral reagents, products and the protonated forms of zwitterionic Baylis-Hillman intermediates with cations and anions of ionic liquids were gently and efficiently transferred directly from the solution to the gas phase. Mass measurements and structural characterization of these unprecedented species via collisioninduced dissociation in tandem mass spectrometry experiments were performed. 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Phosphine-free Heck Reaction: Mechanistic Insights And Catalysis "on Water" Using A Charge-tagged Palladium Complex

A novel Pd-complex with a charge tag (imidazolium cation) was applied for online monitoring of the neutral Heck reaction by electrospray ionization (tandem) mass spectrometry-ESI-MS(/MS). The results shed light on the mechanism of the reaction, whereas the charge-tagged ligand also allowed the unprecedented MS monitoring of Pd2+ reduction to Pd0. Key reaction intermediates associated with Pd catalysis could also be detected and characterized due to the presence of the charge tag on the Pd-complex. DFT calculations supported the proposed mechanism. The new charge-tagged Pd-complex is also shown to function as an active catalyst "on water" with the advantage of using cheaper and less reactive aryl chloride substrates in a phosphine-free version of the Heck reaction. © the Partner Organisations 2014.38729582963Kandukuri, S.R., Schiffner, J.A., Oestreich, M., (2012) Angew. Chem., Int. Ed., 51, pp. 1265-1269Faulkner, A., Bower, J.F., (2012) Angew. Chem., Int. 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The Catalytic Mechanism Of Indole-3-glycerol Phosphate Synthase (igps) Investigated By Electrospray Ionization (tandem) Mass Spectrometry

An enzymatic reaction has been monitored by on-line direct infusion electrospray ionization (tandem) mass spectrometry. Using this fast and sensitive technique, a key and transient intermediate of Mycobacterium tuberculosis indole-3-glycerol phosphate synthase (IGPS)-catalyzed reaction has been trapped. The reaction catalyzed by indole-3-glycerol phosphate synthase is part of the tryptophan biosynthetic pathway, and is not present in mammals, including humans. This peculiarity renders this enzyme a potential target for the development of biospecific agents with potential anti-TB activity. The present results indicate the presence of two intermediates in the mechanism of this enzymatic reaction. © 2008 Elsevier Ltd. All rights reserved.494159145917Raviglione, M.C., Smith, I.M., (2007) New Engl. J. Med., 356, p. 656World Health Organization. Surveillance, planning, financing, WHO Report, Geneva, Switzerland, WHO/HTM/TB/2005.349, 2005Smith, D.A., Parish, T., Stoker, N.G., Bancroft, G.J., (2001) Infect. Immun., 69, p. 1142Ducati, R.G., Ruffino-Netto, A., Basso, L.A., Santos, D.S., (2006) Mem. Inst. Oswaldo Cruz, 101, p. 697Maartens, G., Wilkinson, R.J., (2007) Lancet, 370, p. 2030Pablos-Mendez, A., Raviglione, M.C., Laszlo, A., Binkin, N., Rieder, H.L., Bustreo, F., Cohn, D.L., Nunn, P., (1998) New Engl. J. Med., 338, p. 1641Deng, H., Murkin, A.S., Schramm, V.L., (2006) J. Am. Chem. Soc., 128, p. 7765Lee, C.E., Goodfellow, C., Javid-Majd, F., Baker, E.N., Lott, J.S., (2006) J. Mol. Biol., 355, p. 784Parry, R.J., (1972) Chemistry of Heterocyclic Compounds in Indoles, Part II, 25. , Houlihan W.J. (Ed), Wiley-Interscience, New York pp 1-64Shivakumar, D.M., Bruice, T.C., (2004) Proc. Natl. Acad. Sci. U.S.A., 101, p. 14379Altamirano, M.M., Blackburn, J.M., Aguayo, C., Fersht, A.R., (2000) Nature, 403, p. 617Eberlin, M.N., (2007) Eur. J. Mass Spectrom., 13, p. 18Hsu, F.F., Turk, J., Owens, R.M., Rhoades, E.R., Russell, D.G., (2007) J. Am. Soc. Mass Spectrom., 18, p. 466Knight, W.B., Swiderek, K.M., Sakuma, T., Calaycay, J., Shively, J.E., Lee, T.D., Covey, T.R., Griffin, P.R., (1993) Biochemistry, 32, p. 2031Kirschner, K., Szadkowski, H., Jardetzky, T.S., Hager, V., (1987) Methods Enzymol., 142, p. 386Hennig, M., Darimont, B.D., Jansonius, J.N., Kirschner, K., (2002) J. Mol. Biol., 319, p. 757noteLapis, A.A.M., Neto, B.A.D., Scholten, J.D., Nachtigall, F.M., Eberlin, M.N., Dupont, J., (2006) Tetrahedron Lett., 47, p. 6775Santos, L.S., Neto, B.A.D., Consorti, C.S., Pavam, C.H., Almeida, W.P., Coelho, F., Eberlin, M.N., Dupont, J., (2006) J. Phys. Org. Chem., 19, p. 731Neto, B.A.D., Lapis, A.A.M., Mancilha, F.S., Vasconcelos, I.B., Thum, C., Basso, L.A., Santos, D.S., Dupont, J., (2007) Org. Lett., 9, p. 4001Russowsky, D., Neto, B.A.D., (2003) Tetrahedron Lett., 44, p. 2923Russowsky, D., Neto, B.A.D., (2004) Tetrahedron Lett., 45, pp. 1437-1440Pilli, R.A., Robello, L.G., Camilo, N.S., Dupont, J., Lapis, A.A.M., Neto, B.A.D., (2006) Tetrahedron Lett., 47, p. 166

Facts, Presumptions, And Myths On The Solvent-free And Catalyst-free Biginelli Reaction. What Is Catalysis For?

The current manuscript describes the role and importance of catalysis and solvent effects for the Biginelli multicomponent reaction. The overwhelming number of new catalysts and conditions recently published for the Biginelli synthesis, including in some manuscripts entitled catalyst-free and/or solvent-free have incentivized controversies and hot debates regarding the importance of developing new catalysts and reaction conditions to perform this very important multicomponent reaction. These so-called catalyst-free reports have generated much confusion in the field, requiring urgent elucidations. In this manuscript, we exemplify, demystify, and discuss the crucial role of catalysis, solvent effects, mechanisms, kinetics, facts, presumptions, and myths associated with the Biginelli reaction aiming to avoid current and future confusion and to stimulate new approaches. © 2014 American Chemical Society.79833833397Domling, A., Wang, W., Wang, K., (2012) Chem. 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