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O-hydroxylmethylphenylchalcogens: synthesis, intramolecular nonbonded chalcogen center dot center dot center dot oh interactions, and glutathione peroxidase-like activity

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Title O-hydroxylmethylphenylchalcogens: synthesis, intramolecular nonbonded chalcogen center dot center dot center dot oh interactions, and glutathione peroxidase-like activity
 
Creator TRIPATHI, SK
PATEL, U
ROY, D
SUNOJ, RB
SINGH, HB
WOLMERSHAUSER, G
BUTCHER, RJ
 
Subject chiral selenium electrophiles
effective core potentials
se-c atoms
crystal-structure
organoselenium compounds
antioxidant activity
molecular-structure
divalent selenium
asymmetric methoxyselenenylation
structural-characterization
 
Description The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived from benzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29 was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiated derivative 14 with Se(dtc)(2). Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclic ester derivatives 17 and 24, respectively. Oxidation of selenide 18 with H2O2 affords the spirocyclic compound 19. The presence of intramolecular interactions in dichalcogenides 15 and 22 has been proven by single-crystal X-ray studies. The cyclic compounds 17 and 19 have also been characterized by single-crystal X-ray studies. GP(X)-like antioxidant activity of selenium compounds has been evaluated by the coupled bioassay method. Density functional theory calculations at the mPW1PW91 level on ditelluride 22 have identified a fairly strong nonbonding interaction between the hydroxy oxygen and tellurium atom. The second-order perturbation energy obtained through NBO analysis conveys the involvement of n(O) -> sigma*(Te-Te) orbital overlap in nonbonding interaction. Post wave function analysis with the Atoms in Molecules (AIM) method identified distinct bond critical point in 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 as well as the value of electron density at the bond critical points unequivocally established that a ditelluride could be a better acceptor in nonbonding interaction, when the hydroxy group acts as the donor.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-10-13T23:11:48Z
2011-12-15T09:16:05Z
2011-10-13T23:11:48Z
2011-12-15T09:16:05Z
2005
 
Type Review
 
Identifier JOURNAL OF ORGANIC CHEMISTRY,70(23)9237-9247
0022-3263
http://dx.doi.org/10.1021/jo051309+
http://dspace.library.iitb.ac.in/xmlui/handle/10054/13873
http://hdl.handle.net/100/2986
 
Language en