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| - o-Hydroxylmethylphenylchalcogens: Synthesis, IntramolecularNonbonded Chalcogen···OH Interactions, and GlutathionePeroxidase-like Activity
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| - The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived frombenzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiatedderivative 14 with Se(dtc)2. Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclicester derivatives 17 and 24, respectively. Oxidation of selenide 18 with H2O2 affords the spirocycliccompound 19. The presence of intramolecular interactions in dichalcogenides 15 and 22 has beenproven by single-crystal X-ray studies. The cyclic compounds 17 and 19 have also been characterizedby single-crystal X-ray studies. GPX-like antioxidant activity of selenium compounds has beenevaluated by the coupled bioassay method. Density functional theory calculations at the mPW1PW91level on ditelluride 22 have identified a fairly strong nonbonding interaction between the hydroxyoxygen and tellurium atom. The second-order perturbation energy obtained through NBO analysisconveys the involvement of nO → σ*Te-Te orbital overlap in nonbonding interaction. Post wavefunction analysis with the Atoms in Molecules (AIM) method identified distinct bond critical pointin 15 and 22 and also indicated that the nonbonding interaction is predominantly covalent.Comparison between diselenide 15 and ditelluride 22 using the extent of orbital interaction aswell as the value of electron density at the bond critical points unequivocally established that aditelluride could be a better acceptor in nonbonding interaction, when the hydroxy group acts asthe donor.
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