A Cobalt Mediated Nitrene Transfer aza-Wittig Cascade Reaction to Access 1,3,4-Oxadiazole Scaffolds

Daniël S. Verdoorn; Prabhat Ranjan; Tim De Reuver; Elwin Janssen; Christophe M.L. Vande Velde; Jordy M. Saya; Bert U.W. Maes; Romano V.A. Orru

doi:10.1021/acs.orglett.3c00959

A Cobalt Mediated Nitrene Transfer aza-Wittig Cascade Reaction to Access 1,3,4-Oxadiazole Scaffolds

Daniël S. Verdoorn, Prabhat Ranjan, Tim De Reuver, Elwin Janssen, Christophe M.L. Vande Velde, Jordy M. Saya^*, Bert U.W. Maes^*, Romano V.A. Orru^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

A cobalt(II) mediated three-component synthesis of 5-substituted-N-sulfonyl-1,3,4-oxadiazol-2(3H)-imines using sulfonyl azides, N-isocyaniminotriphenylphosphorane (NIITP), and carboxylic acids has been developed. This one-pot tandem reaction starts with a nitrene transfer to NIITP, followed by addition of the carboxylic acid to the in situ formed carbodiimide and subsequent intramolecular aza-Wittig reaction. Both the steric constraints of carboxylic acid and the stoichiometry of the employed cobalt salt determine the selectivity toward the two products, i.e. 5-substituted-N-sulfonyl-1,3,4-oxadiazol-2(3H)-imine versus 5-substituted-4-tosyl-2,4-dihydro-3H-1,2,4-triazol-3-one.

Original language	English
Pages (from-to)	4005-4009
Number of pages	5
Journal	Organic letters
Volume	25
Issue number	22
Early online date	24 May 2023
DOIs	https://doi.org/10.1021/acs.orglett.3c00959
Publication status	Published - 9 Jun 2023

Bibliographical note

Funding Information:
Research Foundation Flanders (FWO) is acknowledged for financial support (senior research project G0D1921N). P.R. acknowledges the European Union’s Horizon 2021 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 101063688 (project name: SusIsocyanide). We thank Hans Smeets for technical assistance and NMR maintenance (Maastricht University) and Glenn van Haesendonck (University of Antwerp) and Petra Esser (Leibniz-Institut für Interaktieve Materialien) for HRMS measurements.

Publisher Copyright:
© 2023 American Chemical Society.

Funding

Research Foundation Flanders (FWO) is acknowledged for financial support (senior research project G0D1921N). P.R. acknowledges the European Union’s Horizon 2021 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 101063688 (project name: SusIsocyanide). We thank Hans Smeets for technical assistance and NMR maintenance (Maastricht University) and Glenn van Haesendonck (University of Antwerp) and Petra Esser (Leibniz-Institut für Interaktieve Materialien) for HRMS measurements.

Funders	Funder number
European Commission
European Union’s Horizon 2021 research and innovation programme
H2020 Marie Skłodowska-Curie Actions	101063688
Fonds Wetenschappelijk Onderzoek	G0D1921N

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title = "A Cobalt Mediated Nitrene Transfer aza-Wittig Cascade Reaction to Access 1,3,4-Oxadiazole Scaffolds",

abstract = "A cobalt(II) mediated three-component synthesis of 5-substituted-N-sulfonyl-1,3,4-oxadiazol-2(3H)-imines using sulfonyl azides, N-isocyaniminotriphenylphosphorane (NIITP), and carboxylic acids has been developed. This one-pot tandem reaction starts with a nitrene transfer to NIITP, followed by addition of the carboxylic acid to the in situ formed carbodiimide and subsequent intramolecular aza-Wittig reaction. Both the steric constraints of carboxylic acid and the stoichiometry of the employed cobalt salt determine the selectivity toward the two products, i.e. 5-substituted-N-sulfonyl-1,3,4-oxadiazol-2(3H)-imine versus 5-substituted-4-tosyl-2,4-dihydro-3H-1,2,4-triazol-3-one.",

author = "Verdoorn, \{Dani{\"e}l S.\} and Prabhat Ranjan and \{De Reuver\}, Tim and Elwin Janssen and \{Vande Velde\}, \{Christophe M.L.\} and Saya, \{Jordy M.\} and Maes, \{Bert U.W.\} and Orru, \{Romano V.A.\}",

note = "Funding Information: Research Foundation Flanders (FWO) is acknowledged for financial support (senior research project G0D1921N). P.R. acknowledges the European Union{\textquoteright}s Horizon 2021 research and innovation programme under the Marie Sk{\l}odowska-Curie Grant Agreement No. 101063688 (project name: SusIsocyanide). We thank Hans Smeets for technical assistance and NMR maintenance (Maastricht University) and Glenn van Haesendonck (University of Antwerp) and Petra Esser (Leibniz-Institut f{\"u}r Interaktieve Materialien) for HRMS measurements. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

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AU - De Reuver, Tim

AU - Janssen, Elwin

AU - Vande Velde, Christophe M.L.

AU - Saya, Jordy M.

AU - Maes, Bert U.W.

AU - Orru, Romano V.A.

N1 - Funding Information: Research Foundation Flanders (FWO) is acknowledged for financial support (senior research project G0D1921N). P.R. acknowledges the European Union’s Horizon 2021 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 101063688 (project name: SusIsocyanide). We thank Hans Smeets for technical assistance and NMR maintenance (Maastricht University) and Glenn van Haesendonck (University of Antwerp) and Petra Esser (Leibniz-Institut für Interaktieve Materialien) for HRMS measurements. Publisher Copyright: © 2023 American Chemical Society.

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A Cobalt Mediated Nitrene Transfer aza-Wittig Cascade Reaction to Access 1,3,4-Oxadiazole Scaffolds

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