Lewis-Acid-Mediated Intramolecular Cyclization of 4-Aryl-5-allyl-1,2,3-triazoles to Substituted Cyclopentene Derivatives.

4-Aryl-5-allyl--fluoroalkyl-1,2,3-triazoles available by a three-component reaction of fluoroalkyl azides, copper acetylides, and allyl halides underwent aluminum halide-mediated transformation to -(4-halo-2-aryl-cyclopentenyl) imidoyl halides by cyclization of vinyl cation intermediates, followed by halide capture. Utilization of the cyclic products was demonstrated by the synthesis of -alkenyl amides, amidines, isoquinolines, and tetrazoles or by the subsequent modification of the cyclopentene ring.

Ligand-dependent stereoselective Suzuki-Miyaura cross-coupling reactions of β-enamido triflates.

The stereoselective Suzuki-Miyaura cross-coupling of ()-β-enamido triflates is demonstrated. Depending on the nature of the ligand in the palladium catalyst, either retention or inversion of the configuration during the synthesis of β,β-diaryl-substituted enamides is observed. Thus, the method provides synthetic access to both isomers of the target enamides from ()-β-enamido triflates.

Stereoselective Synthesis of ()-β-Enamido Fluorides from -Fluoroalkyl- and -Sulfonyl-1,2,3-triazoles.

A reaction of -sulfonyl-1,2,3-triazole with boron trifluoride etherate afforded a ()-β-ensulfonylamido fluoride instead of the previously erroneously assigned isomer. The correction of the stereochemistry was based on a ge-1D ROESY NMR experiment and X-ray crystal structure analyses. Application of the reaction to -fluoroalkyl-1,2,3-triazoles afforded new ()-β-enamido fluorides in a stereoselective manner.

Stereoselective Synthesis of (Z)-β-Enamido Triflates and Fluorosulfonates from N-Fluoroalkylated Triazoles.

N-Fluoroalkylated 1,2,3-triazoles in the presence of triflic acid or fluorosulfonic acid underwent a cascade reaction consisting of triazole protonation, ring opening, nitrogen elimination, sulfonate addition, HF elimination, and hydrolysis to furnish novel trifluoromethanesulfonyloxy- or fluorosulfonyloxy-substituted enamides, respectively, in a highly stereoselective fashion. The vinyl triflates underwent cross-coupling reactions to a variety of substituted enamides and serve as sources of the aminovinyl cations. In reactions with triflic acid, electron-rich triazoles afforded 2-fluoroalkylated oxazoles.

A rhodium-catalyzed transannulation of N-(per)fluoroalkyl-1,2,3-triazoles under microwave conditions - a general route to N-(per)fluoroalkyl-substituted five-membered heterocycles.

A rhodium-catalyzed transannulation via ring-opening of N-(per)fluoroalkyl-substituted 1,2,3-triazoles followed by cycloaddition with different nitriles, enol ethers, isocyanates and silyl ketene acetals under microwave heating provided a highly efficient route to previously unreported N-(per)fluoroalkyl-substituted imidazoles, pyrroles, imidazolones and pyrrolones, respectively. These reactions were found to be applicable to the synthesis of a variety of 5-membered heterocycles bearing different (per)fluoroalkyl substituents as well as both electron-donating and electron-withdrawing groups attached to the heterocyclic core.

Identification of Eukaryotic Translation Elongation Factor 1-α 1 Gamendazole-Binding Site for Binding of 3-Hydroxy-4(1 H)-quinolinones as Novel Ligands with Anticancer Activity.

Here, we have identified the interaction site of the contraceptive drug gamendazole using computational modeling. The drug was previously described as a ligand for eukaryotic translation elongation factor 1-α 1 (eEF1A1) and found to be a potential target site for derivatives of 2-phenyl-3-hydroxy-4(1 H)-quinolinones (3-HQs), which exhibit anticancer activity. The interaction of this class of derivatives of 3-HQs with eEF1A1 inside cancer cells was confirmed via pull-down assay.