Unveiling the molecular mechanisms of the cycloaddition reactions of aryl hetaryl thioketones and C,N-disubstituted nitrilimines.

摘要: Many synthetic routes to constructing biologically active heterocyclic compounds are made feasible through the (3 + 2) cycloaddition (32CA) reactions. Due a large number of possible combinations several heteroatoms from either three-atom components (TACs) or ethylene derivatives, potential 32CA reactions in syntheses is versatile. Herein, reaction thiophene-2-carbothialdehyde derivatives and C,N-disubstituted nitrilimines have been studied density functional theory (DFT) calculations at B3LYP/6-311G(d,p) level theory. In present study, one-step two-step (4 + 3) (43CA) mechanisms involved TACs derivative investigated. all considered, preferred over 43CA. The TAC chemoselectively adds across thiocarbonyl group fashion form corresponding cycloadduct. Analysis electrophilic $$ {P}_K^{+} $$ nucleophilic {P}_K^{-} Parr functions various centers show that atomic with largest functions, which total agreement experimental observation. selectivities observed titled kinetically controlled.