A new
method was developed for the synthesis of 4-chalcogenyl-1H-isochromen-1-ones through the 6-endo-dig electrophilic cyclization of 2-alkynylaryl esters and
diorganyl dichalcogenides under ultrasound irradiation. The reactions
were performed under mild conditions, using Oxone as a green oxidant
to promote the cleavage of the chalcogen–chalcogen bond in
diorganyl diselenides and ditellurides to generate electrophilic species in situ. A total of 25 compounds were selectively obtained
after 30–70 min, in good to excellent yields (74–95%).
This procedure was extended to prepare 5H-selenopheno[3,2-c]isochromen-5-ones. Additionally, for the first time, the
4-chalcogenyl-1H-isochromen-1-ones were used as substrates
in the thionation reaction, using Lawesson’s reagent and microwave
irradiation under solvent-free conditions, obtaining the thio derivatives
in yields of up to 99% in only 15 min.
Herein we present an alternative and transition-metal-free procedure to access 3-organoselanylthiochromones and 3-organoselanylchromones from the cyclization reaction between alkynyl aryl ketones and diorganyl diselenides promoted by Oxone®.
A visible light‐mediated protocol was developed for the construction of 3‐sulfenylthiochromenones by a radical annulation of ortho‐thioaryl ynones. The reaction is triggered by a sulfur‐centered radical, which is formed through the light excitation of an intramolecular electron donor‐acceptor complex (EDA‐complex). A total of twenty‐one compounds were prepared, in poor to excellent yields (28–98 %), sixteen of which are unprecedented. The reactions were conducted under open‐air conditions, not requiring metal catalysts, oxidant species, or heating, making this a mild and environmentally friendly approach to access valuable compounds.
A metal-and catalyst-free photo-promoted cyclization of properly substituted vinyl selenides was developed using UVA irradiation. A total of eighteen new C3-unsubstituted 2-selanyl benzochalcogenophenes (benzofurans, benzothiophenes and benzoselenophenes) were prepared in 30-86% yield after irradiation with UVA at room temperature.The usefulness of the title compounds was demonstrated in the easy functionalization of the remaining free CÀ H bond of the benzochalcogenophenes to form new CÀ Se and CÀ Br bonds by simple procedures. Furthermore, the reaction can be performed under natural sunlight irradiation and the solvent is easily reused further in several subsequent runs.
The Cover Feature shows the office environment of an organic synthesis laboratory, centered around a “synthetic tools desk,” which is a place where ideas are discussed on a daily basis. In their Research Article, R. H. Bartz et al. demonstrated one of the few cases in which an intramolecular EDA‐complex (the molecule on the desk) is used as a species that can absorb blue light (440 nm) and trigger an annulative radical process. In this sophisticated synthetic transformation, thiols are used as reactants, giving rise to the “most wanted” 3‐sulfenylthiochromones. This strategy circumvents the classical use of photocatalytic species in light‐mediated reactions, as well as the use of oxidants and heating, readily yielding the desired products in a short reaction time. Taken together, the main features of the developed approach meet some principles of green chemistry and promote sustainable chemistry. More information can be found in the Research Article by R. H. Bartz et al.
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