In the presence of Pd(II) salts, substitution reaction of aryl halides with potassium cyanide occurs readily which affords a simple and beneficial method for aryl cyanide synthesis.

No abstract

The displacement reaction of various non-activated aryl halides with cyanide ions was investigated in the presence of palladium salts. Various aryl iodides and bromides were converted into the corresponding aryl cyanides in good yields under mild conditions. The addition of certain substances, such as potassium hydroxide and potassium carbonate, enhanced the catalytic activity. Hexamethylphosphoric triamide, in which potassium cyanide was scarcely soluble, was an outstanding solvent for the reaction. The reduced palladium species was supposed to be the active catalyst.

portions of water, 10% sodium thiosulfate solution, saturated sodium bicarbonate solution, and saturated sodium chloride. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated by rotary evaporation to afford 1.11 g of a yellow oil. The oil was eluted through a silica column with dichloromethane, and the solvent was removed by rotary evaporation. Recrystallization from hot methanol afforded 480 mg (55%) of iodide 17-2-d as colorless needles: mp 47-48 °C; 0% d0, 100% di.

Optically active '--methylbenzyl-l-propyl-2,4-dimethyl-1,4-dihydronicotinamide, a chiral model of NAD(P)H, has been synthesized and its absolute configuration has been determined. It has been found that the model compound exerts high enantiospecificity in the reduction of certain carbonyl compounds in the presence of magnesium perchlorate. The results seem to show that the enantiospecificity is controlled by both the electronic and steric effects of substituents in the carbonyl compounds. The polar substituent of the substrate undergoing reduction faces the carbamoyl group of the model compound in the transition state for the reaction.