One‐Pot Selective Syntheses of 5‐Azaindoles through Zirconocene‐Mediated Multicomponent Reactions with Three Different Nitrile Components and One Alkyne Component

5‐Azaindoles either with three different substituents at their 2‐, 4‐, and 6‐positions or with two identical substituents at their 2‐ and 6‐positions and a different one at the 4‐position, were obtained in good to excellent isolated yields by a zirconocene‐mediated multicomponent process. Each reaction involved four organic partners, comprising a Si‐tethered diyne, one t BuCN component, and two (either different or identical) nitriles. All these four components were combined through the action of a Cp 2 Zr II species into a three‐ring fused Zr/Si‐containing organometallic complex in a perfectly chemo‐ and regioselective manner. This multicomponent reaction process consisted of three reaction steps, all of which were made clear through the isolation and characterization of their corresponding organometallic intermediates: the zirconacyclopropene‐azasilacyclopentadienes 2 , the allenyl‐aza‐zirconacycles 3 , and the three‐ring fused complexes 6 . X‐ray single‐crystal structural analyses of two three‐ring fused Zr/Si‐containing intermediates and two 5‐azaindoles unambiguously showed the positions of the different substituents and the regioselectivity. Iminopyrrole derivatives could be also highly selectively prepared from a Si‐tethered diyne and two different nitriles.