Efficient, Functional Group‐Tolerant, and Catalyst‐Free Nitrile Formation from Aldehydes

Chemistry - A European Journal, vol. 31, pp. e02629

Abstract

Abstract The development of efficient methods for nitrile syntheses is a challenge due to the current reliance on toxic cyanide sources, metal catalysts and their associated waste products, and harsh conditions that limit functional group compatibility. Here, we show a metal‐ and complex reagent‐free strategy for the conversion of aldehydes to nitriles through carbamoylaldoxime intermediates. Therefore, we synthesize aldoximes from several aldehydes using hydroxylamine, which in turn are reacted with dimethylcarbamoyl chloride (DMCC) to afford N,N‐ dimethylcarbamoyloximes. Subsequent heating cleanly produces the desired nitriles as well as volatile CO 2 and HNMe 2 through a pericyclic syn elimination. This approach relies on widely available commercial chemicals, proceeds with broad functional group tolerance, and minimizes the need for extensive purification of the nitrile product.

Authors 3

1. Simay Aydonat Aachen Institute of Technical and Macromolecular Chemistry

   RWTH Aachen University · DWI – Leibniz Institute for Interactive Materials · University of Wuppertal

   Affiliation as printed

   DWI – Leibniz Institute for Interactive Materials Forckenbeckstr. 50 52056 Aachen Germany

   Department of Chemistry and Biology University of Wuppertal Gaußstr. 20 42119 Wuppertal Germany

   Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 52074 Aachen Germany

   Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany

2. Davide Campagna Aachen Institute of Technical and Macromolecular Chemistry

   RWTH Aachen University · DWI – Leibniz Institute for Interactive Materials

   Affiliation as printed

   DWI – Leibniz Institute for Interactive Materials Forckenbeckstr. 50 52056 Aachen Germany

   Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 52074 Aachen Germany

   Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, Germany

3. Robert Göstl corresponding Aachen

   DWI – Leibniz Institute for Interactive Materials · University of Wuppertal

   Affiliation as printed

   DWI – Leibniz Institute for Interactive Materials Forckenbeckstr. 50 52056 Aachen Germany

   Department of Chemistry and Biology University of Wuppertal Gaußstr. 20 42119 Wuppertal Germany