A metal-free dual photo- and organocatalytic decarbonylation of aliphatic aldehydes is described for the first time. On the one hand, a wide range of tertiary aldehydes are smoothly decarbonylated thanks to the combination of thioxanthone as photocatalyst and diphenyl disulfide as organocatalyst. On the other hand, by simply using 4-CzIPN as photocatalyst instead of thioxanthone, various secondary aldehydes readily undergo decarbonylation in an orthogonal manner, via the in situ formation of 1,4-dihydropyridines. Both methodologies are compatible with various functional groups and are readily applied to the decarbonylation of complex molecules.
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http://dx.doi.org/10.1002/anie.202424459 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Université Paris-Saclay: Universite Paris-Saclay, BioCIS, UMR 8076, 17 avenue des sciences, 17 avenue des sciences, 91405, Orsay, FRANCE.
A metal-free dual photo- and organocatalytic decarbonylation of aliphatic aldehydes is described for the first time. On the one hand, a wide range of tertiary aldehydes are smoothly decarbonylated thanks to the combination of thioxanthone as photocatalyst and diphenyl disulfide as organocatalyst. On the other hand, by simply using 4-CzIPN as photocatalyst instead of thioxanthone, various secondary aldehydes readily undergo decarbonylation in an orthogonal manner, via the in situ formation of 1,4-dihydropyridines.
View Article and Find Full Text PDFJ Org Chem
December 2021
Université de Nantes, CNRS, CEISAM UMR 6230, F-44000 Nantes, France.
The discovery of a multiple-bond-forming process merging the singlet oxygen-mediated dearomatization of 3,4-disubstitued phenols and diastereo- and regioselective epoxidation is described. This one-pot strategy using a transition metal-free multicatalytic system comprised of rose bengal and cesium carbonate allowed the efficient formation of functionalized epoxyquinol products under mild conditions. Mechanistic investigations have been performed to shed the light on the key species involved in this transformation.
View Article and Find Full Text PDFJ Org Chem
August 2017
Institut für Organische Chemie, Universität Leipzig, Johannisallee 29, D-04103 Leipzig, Germany.
An NHC-catalyzed nitro-Stetter/elimination/Stetter reaction sequence employs nitroalkenes as latent 1,2-dication synthons providing a novel access to highly useful symmetrical and unsymmetrical 2-aryl substituted 1,4-diketone building blocks from commercially available aldehyde precursors. For less activated (aliphatic) aldehydes, a cooperative catalytic strategy has been developed via the merger of NHC and H-bonding catalysis. To further showcase the versatility of our approach, a great variety of these unprecedented 1,4-diketones are used to efficiently synthesize polysubstituted pyrroles-including those with hetaryl substituents-in good to excellent yields in a multicatalytic metal-free, four-step one-pot cascade reaction under mild, yet robust, conditions.
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