title: Diverse Reactions of Thiophenes, Selenophenes, and Tellurophenes with Strongly Oxidizing I(III) PhI(L)2Reagents.
abstract: We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr)2][OTf]2(Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either -IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr)2][OTf]2gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.
authors.affiliation: Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University , Melbourne, Victoria, Australia , 3086.
authors.forename: Sathsara
authors.initials: S
authors.lastname: Egalahewa
authors.affiliation: Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University , Melbourne, Victoria, Australia , 3086.
authors.forename: Mohammad
authors.initials: M
authors.lastname: Albayer
authors.affiliation: Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University , Melbourne, Victoria, Australia , 3086.
authors.forename: Antonino
authors.initials: A
authors.lastname: Aprile
authors.affiliation: Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University , Melbourne, Victoria, Australia , 3086.
authors.forename: Jason L
authors.identifier: http://orcid.org/0000-0002-0361-4441
authors.initials: JL
authors.lastname: Dutton