Origins of the Reactivity in 1,3-Dipolar Cycloadditions of Acyl Isocyanide Ylides |
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| Authors: | Javier E Alfonso-Ramos Ruben Van Lommel David Hernández-Castillo Prof Frank De Proft Roy González-Alemán Prof Erik V Van der Eycken Gerardo M Ojeda-Carralero |
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| Institution: | 1. Laboratory of Computational and Theoretical Chemistry (LQCT) Faculty of Chemistry, University of Havana Zapata y G, 10400 Havana, Cuba;2. Molecular Design and Synthesis, Department of Chemistry, KU Leuven Celestijnenlaan 200F Leuven Chem&Tech, box 2404, 3001 Leuven, Belgium;3. Eenheid Algemene Chemie (ALGC) Department of Chemistry, Vrije Universiteit Brussel (VUB) Pleinlaan 2, 1050 Brussels, Belgium;4. Laboratory for Organic & Microwave-Assisted Chemistry (LOMAC), Department of Chemistry, KU Leuven Celestijnenlaan 200F Leuven Chem&Tech, box 2404, 3001 Leuven, Belgium |
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| Abstract: | 1,3-Dipolar cycloadditions are the preferred method to generate five-membered heterocyclic rings. Surprisingly, cycloadditions based on acyl-isocyanide ylides have remained underexplored by the chemical community. Acyl-isocyanide ylides readily react with dipolarophiles, such as substituted alkenes, to yield Δ1-pyrroline derivatives. As an explanation for the observed reactivity of this reaction is lacking, extensive density functional theory calculations were performed to scrutinize the mechanistic features of the transformation. Herein we explain the experimental outcome of the reaction using a variety of reactivity theories and predict opposed regioselectivity for electron-poor and electron-rich dipolarophiles. With the insights obtained, we hope to incentivize the design of new cycloaddition reactions based on the acyl-isocyanide ylides motif. |
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| Keywords: | 1 3-dipolar cycloaddition acyl isocyanide ylides density functional theory regioselectivity |
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