AgNTf₂-Catalyzed Regioselective C–H Alkenylation of N,N-Dialkylanilines with Ynamides

Abstract

Regioselective C–H alkenylation of N,N-dialkylanilines with ynamides was developed using AgNTf2 as a catalyst. This approach represents a facile hydroarylation of ynamides, allowing for the introduction of an alkenyl group exclusively at the para position of aniline derivatives. As a result, a series of 4-alkenyl N,N-dialkyl­anilines were synthesized with excellent regioselectivities.

AgNTf2 catalyzed cycloaddition of N-acyliminium ions with alkynes for the synthesis of the 3,4-dihydro-1,3-oxazin-2-one skeleton

“…When AgSbF 6 was examined, the desired 3aa was obtained in 31% yield (Table 1, entry 12). Delightfully, a catalytic amount of AgNTf 2 30 could significantly increase the yield of 3aa to 72% (Table 1, entry 13). A higher reaction temperature resulted in a lower yield (56%) of 3aa (Table 1, entry 14).…”

Catalytic intermolecular hydrofunctionalizations of ynamides

“…Recently, Wei and Si found that when N , N -dialkylanilines were employed as coupling partners, AgNTf 2 was demonstrated to be a better catalyst for the hydroarylation of ynamides and syn -adducts were obtained as the main products (Scheme 18). 45 In the presence of a cationic silver catalyst, the ynamide is first converted into the three-membered silver complex Int-32 , which further undergoes rearrangement to form the silver keteniminium species Int-33 . Subsequently, nucleophilic attack of the para -C atom of the aniline at the α-site of keteniminium yields the α-aryl vinyl silver intermediate.…”