A new synthetic approach to porphyrin-acetylene and porphyrin-diene derivatives utilizing tetraphenylporphyrin (TPP) and two new reactions (vicarious nucleophilic substitution and metathesis) is described. 5-(4-Nitrophenyl)-10,15,20-triphenylporphyrin zinc complex reacts with - CHXY type carbanions, affording the nucleophilic substitution of hydrogen products containing CH 2 SO 2 Tol, CH 2 SO 2 Ph, CH 2 SO 2 NMe 2 , and CH 2 CN groups, respectively. The products obtained when alkylated with alkyl halides, bearing an acetylenic function in the terminal position, resulted in the formation of TPP-acetylene building blocks. These systems were subjected to cross-enyne metathesis reaction with ethylene (with the use of efficient ruthenium catalysts) to give the porphyrin-diene dyads - the excellent substrates for further transformations.