The formation of C-N bonds with aryl amines is one of the most widely studied reactions in organic chemistry. Despite this, it is still highly challenging, often requiring expensive, precious metal-based catalysts. Here we report an easy catalyst-free methodology for constructing C-N bonds. The method, which proceeds via the in situ formation of closed ring amidinium ions, allows the preparation of a series of symmetrical and/or unsymmetrical aryl diamines in notably high yields (82-98%) and purity and with a variety of different substituents. The methodology is shown successful for the preparation of aryl diamines having para- and/or meta-substituted carboxyl, nitro, bromo, methoxy, or methyl groups. This green synthetic pathway, which is catalyst free, requires only three steps, and proceeds without the need for purification. Further, it is a new sustainable, economically viable method to achieve an otherwise challenging bond formation.