Affiliation:
1. Department of Chemistry Central Tehran Branch Islamic Azad University Tehran Iran
2. Department of Chemistry South Tehran Branch Islamic Azad University Tehran 11-TS2 Iran
Abstract
AbstractDFT calculations at M062X/6‐31+G(d,p) and M062X/Def2SVP levels of theory were utilized to explore the mechanism and cycloisomerization of 15‐membered triazaenediyne macrocycles in gas phase and Toluene. Trans triazaenediyne conducted concerted reactions to produce a trans diastereoselective tetracyclic fused structure passing through key cascade reactions starting by an Ene reaction that produced an allene intermediate (ΔG#=37.37 kcal/mol), and following a Diels‐Alder reaction which converted to trans‐tetracyclic ring overcoming a 34.10 kcal/mol barrier. In catalytic Rh (I), two steps reactions converted reagent to a diastereoselective trans‐cyclohexadiene tetracyclic by vanquishing barriers of 30.75 and 22.66 kcal/mol.