title: Synthesis and structural characterization of pincer type bicyclic diacyloxy- and diazaselenuranes.
abstract: Synthesis and structural characterization of a new class of pincer type bicyclic diacyloxy- and diazaselenuranes is reported. The reaction of dimethyl 2-bromo-5-tert-butylisophthalate (28) with sodium benzeneselenolate affords the corresponding monoselenide, dimethyl 5-tert-butyl-2-(phenylselanyl)isophthalate (29). Reduction of 29 with LiAlH(4) provides 5-tert-butyl-2-(phenylselanyl)-1,3-phenylene)dimethanol 31. Oxidation of 29 or its hydrolyzed derivative, 5-tert-butyl-2-(phenylselanyl)isophthalic acid (30), with H(2)O(2) results in the formation of bicyclic diacyloxyselenurane (25). The reaction of 30 with aniline using the DCC coupling reaction gives 5-tert-butyl-N(1),N(3)-diphenyl-2-(phenylselanyl)isophthalamide (38). Reaction of 38 with H(2)O(2) leads to the formation of the corresponding bicyclic diazaselenurane (27) via selenoxide intermediate 39. Compounds 25, 27, 29 and 31 were characterized by single crystal X-ray crystallography. The structural aspects of the pincer type bicyclic chalcogenuranes are investigated using experimental and computational studies and compared with the related systems.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, India.
authors.forename: K
authors.initials: K
authors.lastname: Selvakumar
authors.forename: Harkesh B
authors.initials: HB
authors.lastname: Singh
authors.forename: Nidhi
authors.initials: N
authors.lastname: Goel
authors.forename: Udai P
authors.initials: UP
authors.lastname: Singh
authors.forename: Ray J
authors.initials: RJ
authors.lastname: Butcher
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D008958:Models, Molecular; D015394:Molecular Structure; D016566:Organoselenium Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D016566:Organoselenium Compounds