Facile N-arylation of amidines and N,N-disubstituted amidines

Synthesis of Stannylated Aryl Imines and Amines via Aryne Insertion Reactions into Sn−N Bonds

“…Aryne chemistry offers a transition metal free alternative for arene C−N bond formation (Scheme 1B). Along these lines, aryne insertions into N−H bonds have been reported [18,19] . Further leveraging aryne chemistry, 1,2‐difunctionalized arenes are directly accessible through σ‐insertion reactions into element‐element bonds and considering the synthesis of aniline derivatives, the group of Kunai presented 1,2‐aminosilylation of arynes [20] …”

“…Along these lines, aryne insertions into NÀ H bonds have been reported. [18,19] Further leveraging aryne chemistry, 1,2-difunctionalized arenes are directly accessible through σ-insertion reactions into element-element bonds and considering the synthesis of aniline derivatives, the group of Kunai presented 1,2-aminosilylation of arynes. [20] Using the same conceptual approach, aminobenzamides, [21] aminobenzophenones, [22] aminobenzonitriles, [25] sulfinylanilines [26] and haloaminoarenes [27] have been successfully prepared via aryne insertion reactions.…”

“…In THF under otherwise identical conditions, yield dropped to 65 % (entry 14). As compared to 1 b, the triflate 1 a and aryne precursor 1 c delivered lower yields (entry [15][16][17][18][19][20]. Practicality of the process was documented by running the reaction in Et 2 O at 1.0 mmol scale to provide the product 3 b in 82 % isolated yield.…”

“…B) Arene CÀ N bond formation through arynes. [18][19][20][21][22][23][24][25][26][27] C) Aryne insertion into the NÀ Sn bond of a stannylated benzophenone imine. The scope with respect to the aryne component was studied next using imine 2 b as the amination reagent (Scheme 4).…”

A Highly Efficient Copper-Catalyzed Three-Component Synthesis of 4-Aminoquinazolines

“…Further investigations indicated that both CuBr and L-proline were necessary for this transformation ( Table 1, entries 12 and 13). Moreover, replacing NaN 3 with other nitrogen sources such as ammonium acetate, ammonium hydroxide and ammonium chloride, gave unsatisfactory results ( Table 1, entries [14][15][16]. Subsequently, the effect of different solvents was investigated, and DMF proved to be the optimum solvent ( Table 1, compare entries 2 and 17-21).…”