Copper-Catalyzed Domino Halide Exchange-Cyanation of Aryl Bromides

Abstract

An efficient copper-catalyzed domino halogen exchange-cyanation procedure for aryl bromides was developed utilizing 10 mol % CuI, 20 mol % KI, 1.0 equiv of the inexpensive N,N'-dimethylethylenediamine as ligand, and 1.2 equiv of NaCN in toluene at 110 degrees C. The new method represents a significant improvement over the traditional Rosenmund-von Braun reaction: the reaction conditions are much milder, and the use of stoichiometric amounts of copper(I) cyanide and polar solvents is avoided; therefore the isolation and purification of the aromatic nitrile products is greatly simplified. In addition, the new method exhibits excellent functional group compatibility comparable to that of the analogous Pd-catalyzed cyanation methodology.

Silica supported heteropolyacid catalyzed dehydration of aldoximes to nitriles and alcohols to alkenes

“…BET surface area measurements were carried out by nitrogen adsorption (Micromeritics ASAP 2010) at an adsorption temperature of 77 K. The FTIR spectra were recorded using a Perkin Elmer (Spectra 100) spectrometer by KBr pellet technique. 1 H NMR and 13 C NMR spectra were recorded on JEOL-300 MHz NMR spectrometer using TMS as an internal standard. GCÁMS spectra were recorded on Schimatzu-QP2010.…”

Modern Synthetic Approaches to Phthalonitriles with Special Emphasis on Transition-Metal Catalyzed Cyanation Reactions

“…and CuI (5.5 mol.%) in the presence of Pd(PPh 3 ) 4 (60 mol.%) and N,N-dimethylethylenediamine (DMEDA, 20 mol.%) in diglyme (Figure 12). [43] Under these conditions coppercatalyzed substitution of bromine with iodine occurs, [44] with subsequent Pd-catalyzed cyanation, which altogether affords target tetranitrile in 51 % yield. Copper or zinctemplated cross-condensation of this tetranitrile with excess of tert-butyl-phthalonitrile afforded dimeric phthalocyanines with efficient transannular interaction in the excited singlet states.…”

Mechanistic Aspects of Metal‐Catalyzed C—C and C—X Bond‐Forming Reactions

“…Cu(II) also catalyzes the reaction of boronic acids with phenols and amines under oxidative conditions to form Ar-O and Ar-N bonds [226]. Copper also catalyzes the halogen exchange [227] and the cyanation [228] of aryl halides. Interestingly, important differences exists between the Pdand Cu-catalyzed amination [229].…”