Five-Component [2 + 2 + 1 + 1] Tandem Benzannulation\nLeading to Multifunctionalized Aromatic Amines

An\nunprecedented five-component [2 + 2 + 1 + 1] benzannulation\nstrategy for regioselective assembly of densely functionalized aromatic\namines from two ynals, two malononitriles, and sodium sulfinates is\nestablished. The benzannulation protocol enables the efficient installation\nof five substituents on a benzene ring via the formation of multiple\nchemical bonds in a single operation, providing various multifunctionalized\naromatic primary amines in moderate to good yields. Additionally,\nthree-component [3 + 2 + 1] cycloaddition of malononitriles, ynals,\nand NH<sub>4</sub>SCN was also achieved to produce 2-amnopyridine\nderivatives with NH<sub>4</sub>SCN serving as an ammonia surrogate.