Origins of the Reactivity in 1,3-Dipolar Cycloadditions of Acyl Isocyanide Ylides

Javier E. Alfonso-Ramos, Ruben Van Lommel, David Hernandez-Castillo, Frank De Proft, Roy Gonzalez-Aleman, Erik V. Van der Eycken, Gerardo M. Ojeda-Carralero

Onderzoeksoutput: Articlepeer review

2 Downloads (Pure)

Samenvatting

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.

Originele taal-2English
Artikelnummere202201028
Aantal pagina's8
TijdschriftEuropean Journal of Organic Chemistry
Volume26
Nummer van het tijdschrift3
DOI's
StatusPublished - 17 jan 2023

Bibliografische nota

Funding Information:
G.M.O.C. is grateful to VLIR-UOS for financial support of a Flemish-Cuba cooperation project (CU2018TEA458A101, recipient G.M.O.C., management, conceptualization and writing). J.E.A.R., D.H.C. and R.G.A. acknowledge the support of the International Fund and Project Management Office from the Ministry of Science, Technology and Environment, Republic of Cuba (project PN223LH010-02X, recipient J.E.A.R., experiments, data analysis and writing, and D.H.C. and R.G.A., revision of manuscript and technical support). R.V.L. acknowledges the use of Tier2 computational resources and services provided by the Shared ICT Services Centre funded by the Vrije Universiteit Brussel, the Flemish Supercomputer Center (VSC), and FWO. R.V.L. thanks FWO for the Ph.D. fellowships received (1185221 N, recipient R.V.L., experiments, writing, data analysis and visualization). E.V.V.d.E. is thankful to “RUDN University Strategic Academic Leadership Program” for financial support. The publication has been prepared with the support of the «RUDN University Strategic Academic Leadership Program» (recipient EVdE, supervision and writing). F.D.P. wishes to acknowledge the Vrije Universiteit Brussel for the support through a Strategic Research Program (supervision and revision of manuscript).

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Copyright:
Copyright 2023 Elsevier B.V., All rights reserved.

Vingerafdruk

Duik in de onderzoeksthema's van 'Origins of the Reactivity in 1,3-Dipolar Cycloadditions of Acyl Isocyanide Ylides'. Samen vormen ze een unieke vingerafdruk.

Citeer dit