Continuing in our researches on the syntheses, reactivity, pharmacological/biological activities of heterocyclic compounds containing one or more nitrogen atoms we have examined some chemico-physical properties (1H and 13C NMR, electrochemical behavior, ESR) three series 2-aryl-5(or 6)-nitrobenzimidazoles (1–3) variously substituted 2-aryl ring. The behavior nitro group benzimidazole ring has b...

The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century1 organic chemists have sought to develop new and more efficient aryl-aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl-aryl bonds, arguably the most common method is through the use of transition-...

(Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesi...

The electronic properties of polyhedral oligomeric silsesquioxanes (POSS) have recently been subjected to study. Although theoretical calculations have predicted that POSS can work as an acceptor for π-conjugated organic units, an effective reaction to incorporate aryl groups into a POSS backbone remains to be established. In this work, Rh-catalyzed direct arylation has been developed. Heptaiso...

N(1)-Arylsulfonyl-substituted analogs of N,N-dimethyltryptamine bind at 5-HT(6) receptors. Replacement of the aryl moiety with similarly hydrophobic alkyl substituents results in decreased affinity, as does replacement of a benzenesulfonyl moiety with a benzyl group. Current findings indicate that an aryl (or substituted aryl) sulfonyl (rather than alkylsulfonyl or benzyl) moiety is optimal for...

P,N,N-Pincer nickel complexes [Ni(Cl){N(2-R2PC6H4)(2'-Me2NC6H4)}] (R = Ph, 3a; R = Pr(i), 3b; R = Cy, 3c) were synthesized and their catalysis toward the Kumada or Negishi cross-coupling reaction of aryl fluorides and chlorides was evaluated. Complex 3a effectively catalyzes the cross-coupling of (hetero)aryl fluorides with aryl Grignard reagents at room temperature. Complex 3a also catalyzes t...

Trans- and cis-2-aryl-3-(2-cyanoethyl)aziridines, prepared via alkylation of the corresponding 2-aryl-3-(tosyloxymethyl)aziridines with the sodium salt of trimethylsilylacetonitrile, were transformed into variable mixtures of 4-[aryl(alkylamino)methyl]butyrolactones and 5-[aryl(hydroxy)methyl]pyrrolidin-2-ones via KOH-mediated hydrolysis of the cyano group, followed by ring expansion. In additi...

Density functional theory has been used to investigate various solvated species that may be formed from palladium bis N-heterocyclic carbene complexes, [Pd(cyclo-C{NRCH}2)2], (PdL2) in benzene solution. Formation of an g -arene complex is shown to stabilise a monocarbene species, PdL(g-C6H5X), where the arene is either the solvent or a reacting aryl halide. Oxidative addition of an aryl chlorid...

A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C-F reductive elimination from a LPd(II)(aryl)F complex (L = t-BuBrettPhos or RockPhos) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in situ, serves as the actual supporting ligand during catalysis with suc...

A new convenient, functional group-tolerant, transition metal-free route to aryl trifluoromethyl ketones under mild conditions is described. The reaction of not only aryl Grignard reagents carrying reducible electrophilic functional groups, such as ester and cyano groups, but also electron-deficient nitrogen-containing heteroaryl Grignard reagents with methyl trifluoroacetate gives the correspo...