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The review systematizes for the first time literature data of the last 15 years on a synthesis of pyridine bases including those of natural structure with the use of metal complex catalysts. The catalyzed by complexes of transition metals (Co, Ni, Pd, Zr) and rare-earth elements reactions of heterocyclization of acetylenes with nitriles, liquid phase condensation of aldehydes with amines, linear and cyclic oligomerization of vinylpyridines with 1,3-dienes and condensation of carbonic acid chloroanhydrides with olefins, acetylenes, tertiary alcohols to give substituted pyridines, quinolines and phenanthrolines of a set structure are considered. The mechanisms of molecule generation of pyridine bases in the presence of metal complex catalysts are discussed, and data on an effect of transition metal nature, initial monomer structure and reaction conditions on a reaction direction of a formation of six-membered nitrogen heterocycles are listed.

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Cocondensation of the (het)aromatic aldehydes (I) with butyraldehyde (II) in the presence of urea (III) and a Co(II)/triethylaluminum catalytic system gives the (het)arylpyridines (IV), together with the diethylpropylpyridine (V).

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Reaction of the ethynyl carbinols (I) with the acyl chlorides (II) in the presence of zinc chloride followed by work‐up with ammonia (III) gives the substituted alkylpyridines (IV).

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