In this Letter, triazoles as carbene reagents were used for sulfonamide-directed C-H insertion carbenoid functionalization to construct benzylpyridine sulfonamide dual-pharmacophore compounds. This method is simple and efficient and can be used for the late-stage modification of sulfonamide drugs.
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http://dx.doi.org/10.1021/acs.orglett.9b03904 | DOI Listing |
Int J Mol Sci
January 2025
Research Institute of Chemistry, Peoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia.
In this study, we report the first example of acyclic (amino)(N-pyridinium)carbenoid gold(III) complexes synthesized via a coupling reaction between 2-pyridylselenyl chloride and Au(I)-bound isonitriles. The reaction involves an initial oxidative addition of the Se-Cl moiety to Au(I), followed by the nucleophilic addition of the pyridine fragment to the isonitrile's C≡N bond, furnishing a metallacycle. Importantly, this is the first example of the pyridine acting as a nucleophile towards metal-bound isonitriles.
View Article and Find Full Text PDFChemphyschem
January 2025
Department of Chemistry, Durgapur Government College, West Bengal, Durgapur, 713214, India.
The relative reactivity and cis/trans selectivity of the intramolecular [3+2] cycloaddition (IM32CA) reactions of nitrile oxide (NO), azide (AZ), nitrile sulfide (NS) and nitrile ylide (NY), leading to functionalized heterocycles are studied within the Molecular Electron Density Theory. The kinetically controlled IM32CA reactions are predicted to be cis stereospecific, while the reaction feasibility follows the order NY>NS>NO>AZ with the respective activation Gibbs free energies of 13.7, 17.
View Article and Find Full Text PDFMolecules
December 2024
State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engneering, Shihezi University, Shihezi 832003, China.
In the category of drugs approved by the U.S. FDA, pyrrolidine is the most frequently used core of five-membered nonaromatic heterocycles containing nitrogen.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
University of Turin - Department of Chemistry, Via Giuria 7, 10125, Turin, Italy.
The chemoselective synthesis of trisubstituted alkenyl halides (Cl, Br, F, I) starting from ketones and aldehydes and lithium halocarbenoids is reported. Upon forming the corresponding tetrahedral intermediate adduct, followed by the addition of thionyl chloride, a selective E2-type elimination is triggered, furnishing the targeted motifs. The transformation takes place under full chemocontrol: various sensitive functionalities ( ester, nitrile, nitro, or halogen groups) can be placed on the starting materials, thus documenting a wide reaction scope, as well as the application of the technique to biologically active substances.
View Article and Find Full Text PDFJ Org Chem
December 2024
Guangdong Provincial Key Laboratory of Chiral Molecules and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China.
A solvent-controlled Rh(III)-catalyzed mono- and dual-C-H bond activation/carbene migratory insertion with diazo compounds as a single coupling partner was demonstrated. The reaction proceeded under mild conditions, yielding products in good to excellent yields. These results are significant for the development of the domino multiple functionalization of C(sp)-H bonds via a carbenoid insertion approach.
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