A novel method for the synthesis of pyrazolo[1,5-a]quinolines under the transition-metal-free conditions has been developed. This method involves a novel combination of aromatic nucleophilic substitution and Knoevenagel condensation reactions to give pyrazolo[1,5-a]quinolines.

The direct replacement of aromatic fluorine in hexafluorobenzene has hitherto been possible only by the use of nucleophilic reagents. In this investigation, the replacement of nuclear fluorine by nonnucleophilic, or weakly nucleophilic, reagents was achieved by reaction at relatively high temperatures, 300 to 850 °C. For example, the reaction of hexafluorobenzene with such reagents as bromine, ...

Kinetic studies of the reactions of α-bromoacetanilides [YC6H4NHC(=O)CH2Br] with substituted benzylamines (XC6H4CH2NH2) have been carried out in dimethyl sulfoxide at 35.0 C. The Hammett plots for substituent (Y) variations in the substrate (log kN vs. σY) are biphasic concave upwards/downwards with breaks at Y = 4-Cl (σY = 0.23). The Hammett coefficients ρY and the cross-interaction constant ρ...

The photoinitiated substitution reactions of anti-7-bromobenzonorbornadiene (5), its syn isomer 6, exo-anti-13-bromobenzocyclobutanorbornene (7), syn-7-bromonorbornene (8) and bromonorbornane (9) with Me(3)Sn(-) and Ph(2)P(-) anions, in liquid ammonia, are here informed to occur with good yields of substitution. The stereochemical outcome is discussed in terms of calculations with the B3LYP fun...

The insertion of a -NO2 group onto the corrole framework represents a key step for subsequent synthetic manipulation of the macrocycle based on the chemical versatility of such a functionality. Here we report results of the investigation of a copper 3-NO2-triarylcorrolate in nucleophilic aromatic substitution reactions with "active" methylene carbanions, namely diethyl malonate and diethyl 2-ch...

In this Account, we describe the development of stereospecific, stereoselective, regioselective, and chemoselective carbon-carbon bond-forming reactions of silacyclopropanes that occur under mild conditions. By appropriate choice of metal salt catalyst, the regiochemistry of these reactions may be tuned to give the desired product. Stereoselective nucleophilic substitution reactions and stereos...

Furfuryl cations are generated via a highly efficient bismuth-catalyzed reaction of furfuryl alcohols. This systematic study provides insight on the reactivity profile of furfuryl cations towards nucleophilic substitution reactions. Novel C-C, C-N, C-O and C-S bond forming reactions of furfuryl cations have been developed, thus providing access to a diverse array of building blocks for further ...

The selectivities of nucleophilic substitution reactions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate depend upon the reaction solvent. Polar solvents favor the formation of S(N)1 products, while nonpolar solvents favor S(N)2 products. Trichloroethylene was identified as the solvent most likely to give S(N)2 products in both C- and O-glycosylation reactions.