Artículos de revistas
Intramolecular hydrogen bond in biologically active o-carbonyl hydroquinones
Molecules 2014, 19, 9354-9368
Martínez Cifuentes, Maximiliano
Weiss López, Boris
Santos, Leonardo S.
Araya Maturana, Ramiro
Intramolecular hydrogen bonds (IHBs) play a central role in the molecular structure, chemical reactivity and interactions of biologically active molecules. Here, we study the IHBs of seven related o-carbonyl hydroquinones and one structurally-related aromatic lactone, some of which have shown anticancer and antioxidant activity. Experimental NMR data were correlated with theoretical calculations at the DFT and ab initio levels. Natural bond orbital (NBO) and molecular electrostatic potential (MEP) calculations were used to study the electronic characteristics of these IHB. As expected, our results show that NBO calculations are better than MEP to describe the strength of the IHBs. NBO energies (ΔEij (2)) show that the main contributions to energy stabilization correspond to LPσ* interactions for IHBs, O1 …O2-H2 and the delocalization LPπ* for O2-C2 = Cα(β). For the O1 …O2-H2 interaction, the values of ΔEij (2) can be attributed to the difference in the overlap ability between orbitals i and j (Fij), instead of the energy difference between them. The large energy for the LP O2π* C2 = Cα(β) interaction in the compounds 9-Hydroxy-5-oxo-4,8, 8-trimethyl-l,9(8H)-anthracenecarbolactone (VIII) and 9,10-dihydroxy- 4,4-dimethylanthracen-1(4H)-one (VII) (55.49 and 60.70 kcal/mol, respectively) when compared with the remaining molecules (all less than 50 kcal/mol), suggests that the IHBs in VIII and VII are strongly resonance assisted.