Search Results (9)

Supramolecular gels were developed by taking advantage of an assembly of small dipeptides containing pyrrolo-pyrazole scaffolds. The dipeptides were prepared through a robust and ecofriendly synthetic approach from the commercially available starting materials of diazoalkanes and maleimides. By playing with the functionalization of the scaffold, the choice of the natural amino acid, and the stereochemistry, we were able to obtain phase-selective gels. In particular, one peptidomimetic showed gelation ability and thermoreversibility in aromatic solvents at very low concentrations. Rheology tests showed a typical viscoelastic solid profile, indicating the formation of strong gels that were stable under high mechanical deformation. NMR studies were performed, allowing us to determine the conformational and stereochemical features at the base of the supramolecular interactions. Full article

The data obtained by the authors in the field of carbon cluster chemistry, namely the catalytic cycloaddition of sulfur-containing diazo compounds to C₆₀-fullerene under the action of complex Pd catalysts, are summarized. Cycloaddition reactions of diazoalkanes, diazoketones, and diazothioates with C₆₀-fullerene, catalyzed by Pd(acac)₂–PPh₃–Et₃Al, with the selective formation of new sulfur-containing methano-, homo-, and pyrazolinofullerenes, are promising as modern nanosized additives in oils for highly loaded mechanisms. Full article

The synthesis of new insecticidal gem-dimethyspiro-cyclopropanes derived from pyrrolidine-2,3-dione have been described, and their biological effect against different insect species has been evaluated. The presented results demonstrate the excellent insecticidal activity of cyclopropane 5c against Aedes aegypti and Musca domestica. Cyclopropane 5c showed the quickest knockdown and the best killing against Aedes aegypti and Musca domestica compared to trans-chrysanthemic acid and pyrethrin. The biological results of the high insecticidal activity were confirmed by the results of docking. This is evident in the binding affinity obtained for cyclopropane 5c, indicating good binding with an important active amino acid residue of the 5FT3 protein. Full article

The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD), with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity, have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G (d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol⁻¹ in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study establishes the depopulation of the N–N–C core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration. Full article

The mechanism of the carbonylation of diazomethane in the presence of iron–carbonyl–phosphine catalysts has been investigated by means of DFT calculations at the M06/def-TZVP//B97D3/def2-TZVP level of theory, in combination with the SMD solvation method. The reaction rate is determined by the formation of the coordinatively unsaturated doublet-state Fe(CO)₃(P) precursor followed by the diazoalkane coordination and the N₂ extrusion. The free energy of activation is predicted to be 18.5 and 28.2 kcal/mol for the PF₃ and PPh₃ containing systems, respectively. Thus, in the presence of less basic P-donor ligands with stronger $\pi$-acceptor properties, a significant increase in the reaction rate can be expected. According to energy decomposition analysis combined with natural orbitals of chemical valence (EDA–NOCV) calculations, diazomethane in the Fe(CO)₃(phosphine)(η¹-CH₂N₂) adduct reveals a $\pi$-donor–$\pi$-acceptor type of coordination. Full article

The direct C-H functionalization reaction is one of the most efficient strategies by which to introduce new functional groups into small organic molecules. Over time, iron complexes have emerged as versatile catalysts for carbine-transfer reactions with diazoalkanes under mild and sustainable reaction conditions. In this review, we discuss the advances that have been made using iron catalysts to perform C-H functionalization reactions with diazoalkanes. We give an overview of early examples employing stoichiometric iron carbene complexes and continue with recent advances in the C-H functionalization of C(sp²)-H and C(sp³)-H bonds, concluding with the latest developments in enzymatic C-H functionalization reactions using iron-heme-containing enzymes. Full article

Synthesis of new chromium(II) complexes with chelating bis(alkoxide) ligand [OO]^Ph (H₂[OO]^Ph = [1,1′:4′,1′’-terphenyl]-2,2′’-diylbis(diphenylmethanol)) and their subsequent reactivity in the context of catalytic production of carbodiimides from azides and isocyanides are described. Two different Cr(II) complexes are obtained, as a function of the crystallization solvent: mononuclear Cr[OO]^Ph(THF)₂ (in toluene/THF, THF = tetrahydrofuran) and dinuclear Cr₂([OO]^Ph)₂ (in CH₂Cl₂/THF). The electronic structure and bonding in Cr[OO]^Ph(THF)₂ were probed by density functional theory calculations. Isolated Cr₂([OO]^Ph)₂ undergoes facile reaction with 4-MeC₆H₄N₃, 4-MeOC₆H₄N₃, or 3,5-Me₂C₆H₃N₃ to yield diamagnetic Cr(VI) bis(imido) complexes; a structure of Cr[OO]^Ph(N(4-MeC₆H₄))₂ was confirmed by X-ray crystallography. The reaction of Cr₂([OO]^Ph)₂ with bulkier azides N₃R (MesN₃, AdN₃) forms paramagnetic products, formulated as Cr[OO]^Ph(NR). The attempted formation of a Cr–alkylidene complex (using N₂CPh₂) instead forms chromium(VI) bis(diphenylmethylenehydrazido) complex Cr[OO]^Ph(NNCPh₂)₂. Catalytic formation of carbodiimides was investigated for the azide/isocyanide mixtures containing various aryl azides and isocyanides. The formation of carbodiimides was found to depend on the nature of organoazide: whereas bulky mesitylazide led to the formation of carbodiimides with all isocyanides, no carbodiimide formation was observed for 3,5-dimethylphenylazide or 4-methylphenylazide. Treatment of Cr₂([OO]^Ph)₂ or H₂[OO]^Ph with NO⁺ leads to the formation of [1,2-b]-dihydroindenofluorene, likely obtained via carbocation-mediated cyclization of the ligand. Full article

A stereocontrolled approach to the cis-decalin framework of clerodane diterpenes and biologically active quinone sesquiterpenes is reported. Starting from an inexpensive optically pure tetrahydroindanone, Birch reductive alkylation builds two new contiguous chiral centers—one of which is quaternary and all-carbon-substituted. Also featured is a highly regioselective diazoalkane—carbonyl homologation reaction to prepare the 6,6-bicyclic skeleton. Therein, the utility of Sc(OTf)₃ as a mild catalyst for formal 1C insertion in complex settings is demonstrated. Full article

The intramolecular [3+2] cycloaddition (32CA) of alkene-tethered α-silyloxydiazoalkanes provides variable stereoselectivity in generating bicyclic pyrazolines where the silyloxy group is either syn or anti to the newly formed pyrazoline ring. To elucidate the origin of the stereoselectivity, density functional theory (DFT) calculations were carried out for the energy of each transition state structure (TSs) and product. Steric effects were identified as the major determining factors in the diastereoselectivity of the 32CA reaction with regards to substrate structure (cyclic or acyclic α-silyloxydiazoalkanes). Full article