Amide as Nitrogen Source： Amination and Mechanism

Abstract

The mechanism of C-N bond formation with amide as nitrogen source was disclosed. The process included the cleavage of amide C-N bond to form amine and then to construct new C-N bond. With the cooperation of Lewis acid, aryl halides, aryl triflates, boronic acids, aryl siloxanes and azoles could be aminated by amide as nitrogen source.

Preparative-Scale Synthesis of Vedejs Chiral DMAP Catalysts

“…The title compound was prepared according to the literature procedure . Thus, a white suspension of anhydrous ZnCl 2 (15.00 g, 110.1 mmol, 1 equiv) and dimethylamine hydrochloride (17.95 g, 220.1 mmol, 2 equiv; dried by repeated vacuum evaporation of a suspension in anhydrous toluene) in EtOH (360 mL) was stirred at 82 °C.…”

“…Disappointingly, the reaction with liquid HNMe 2 in the presence of catalytic Cu/CuCl did not afford the desired chiral DMAP (entry 7). In contrast, the reaction of ( S , S )- 4b with ZnCl 2 (NHMe 2 ) 2 (HCl) 2 , prepared from ZnCl 2 and Me 2 NH hydrochloride, furnished the desired chiral DMAP ( S , S )- 3b in 71% yield (entry 8) . Unfortunately, the success of the ZnCl 2 -mediated substitution was counterbalanced by experimental difficulties associated with handling the thick suspension of inorganic salts (ca.…”