Activation of Quinolines by Cationic Chalcogen Bond Donors

P. Wonner; T. Steinke; S. M. Huber

doi:10.1055/s-0039-1690110

Synlett, Table of Contents

CC BY-ND-NC 4.0 · Synlett 2019; 30(14): 1673-1678
DOI: 10.1055/s-0039-1690110

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Activation of Quinolines by Cationic Chalcogen Bond Donors

P. Wonner

,

T. Steinke

,

S. M. Huber ∗

Abstract

All articles of this category

^§ Both authors contributed equally

Published as part of the Cluster Organosulfur and Organoselenium Compounds in Catalysis

Abstract

The application of already established as well as novel selenium- and sulfur-based cationic chalcogen bond donors in the catalytic activation of quinoline derivatives is presented. In the presence of selected catalysts, rate accelerations of up to 2300 compared to virtually inactive reference compounds are observed. The catalyst loading can be reduced to 1 mol% while still achieving nearly full conversion for electron-poor and electron-rich quinolines. Contrary to expectations, preorganized catalysts were less active than the more flexible variants.

Key words

chalcogen bonding - Lewis acids - organocatalysis - noncovalent interactions - intermolecular interactions - chalcogens - reduction

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References

References and Notes
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26b General procedure for the synthesis of chalcogeno ureas 11–13: Under an argon atmosphere, the respective bis(benz)imidazolium compound (1 equiv) was added to a Schlenk flask and dissolved in anhydrous methanol (0.17 m; dried for 24 h over molecular sieve). To the solution, elemental selenium powder or sulfur (2.5 equiv) and cesium carbonate (2.5 equiv) were added. The mixture was heated at reflux for 24 h and finally filtered (hot solution) over a short plug of silica and rinsed with CH₂Cl₂. After the solvent was removed, the crude solid was purified by column chromatography (solvents noted for specific compounds). All spectroscopic data are given in the Supporting Information.
26c General methylation procedure for the synthesis of compounds 8–10: Under an argon atmosphere, the respective chalcogenourea compound (1 equiv) was dissolved in anhydrous CH₂Cl₂. Then methyl trifluoromethanesulfonate (2.5 equiv) was slowly added at 0 °C and the reaction mixture was stirred for 24 h at room temperature. After the solvent was removed under reduced pressure, the crude residual was diluted in a little acetonitrile and was precipitated by addition of diethyl ether. The solid was filtered off, washed with diethyl ether and pentane and dried under high vacuum. Alternatively, the solvent was removed, and the residue was washed under sonification several times with ether and pentane. Finally, the respective methylated chalcogenated compound was obtained as colorless solid. All spectroscopic data are given in the Supporting Information.
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Supplementary Material

Supporting Information