6 research outputs found

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

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    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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    Phosphine-free Heck Reaction: Mechanistic Insights And Catalysis "on Water" Using A Charge-tagged Palladium Complex

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    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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