Increasing the reactivity of nitrogen catalysts |
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Authors: | De Rycke Nicolas Couty François David Olivier R P |
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Institution: | Institut Lavoisier-Versailles, UMR 8180, Université de Versailles St-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035, Versailles, France. |
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Abstract: | This review article presents how nitrogen-centred Lewis bases were modified in order to increase their reactivity in catalytic processes. As examples, we focus on alcohol acylation and Morita-Baylis-Hilman reactions in order to showcase the fundamental parameters at play in transformations initiated by catalysts bearing respectively an active sp(2) or sp(3) nitrogen atoms. These two aspects are epitomised by two leading compounds, the Steglich base 4-dimethylaminopyridine (DMAP), and 1,4-diazabicyclo2.2.2]octane (DABCO). Throughout this review, we stress the role played and the information brought by physical organic chemistry. Comprehension of these complex transformations relies on the fundamental knowledge of parameters, such as, nucleophilicity, nucleofugality, Lewis basicity, and crucially also the knowledge of their divergent impacts on each elementary step of the catalytic cycle. |
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Keywords: | acylation kinetics nitrogen bases organocatalysis thermodynamics |
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