Photodimerizations of hydroxy- and benzoylated 4-azachalcones and quantum chemical investigation of the reactions.
Photodimerization reactions of compounds 4-6 gave four new cyclobutane-containing compounds (7-9) with full control over the stereochemistry at the four stereogenic centers. These new cyclobutane-containing compounds had beta-truxinic (7a), delta-truxinic (7b and 9), and epsilon-truxillic (8) structures. However, o-, m-, and p-hydroxy 4-azachalcones (1-3) did not give photochemical cyclization products under any conditions (in solvent or in their solid or molten states). Experimental data suggested the possibility of frontier orbital control over stereochemical behavior, so some theoretical calculations were performed. Full geometrical optimization of compounds 1-9 was performed via DFT B3LYP/6-31(+)G**, and their electronic structures were also investigated. The geometries of the singlet and triplet states were initially optimized by density functional theory (DFT) and the configuration interaction singles (CIS) B3LYP/3-21(+)G** level. An additional calculation was performed for the triplet state using the ground-state geometry. The possible photochemical dimerization products of compounds 7-9 (a-g) and the intrinsic reaction coordinates (IRCs) of the reactions of compounds 4-6 were calculated theoretically by the DFT/3-21(+)G** method. The configurations (reactant, transition state, product, and reaction pathway) corresponding to the stationary points (minima or saddle points) were determined. The intrinsic reaction coordinates were followed to verify the energy profiles that connect each TS to the appropriate local minimum. The dimeric products expected from the calculations coincided with the dimers produced experimentally.
Department of Chemistry, Faculty of Arts and Sciences, Karadeniz Technical University, Trabzon, Turkey. ayasar@bayburt.edu.tr
Ahmet
A
Yaşar
Nuran
N
Yayli
Asu
A
Usta
Nurettin
N
Yayli
D001554:Benzene / Q000737:chemistry*; D002599:Chalcone / Q000737:chemistry*; D019281:Dimerization; D004583:Electrons; D006900:Hydroxylation / Q000528:radiation effects; D008027:Light; D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory; D013816:Thermodynamics
D002599:Chalcone; D001554:Benzene