Adriane Sperança

Regioselective synthesis of isochromenones by iron(III)/PhSeSePh-mediated cyclization of 2-alkynylaryl esters.

A series of 4-Se-(Te, S)-isochromenones and 3-substituted isochromenones were synthesized in good yields via FeCl(3)-mediated cyclization of alkynylaryl esters with different diorganyl dichalcogenides. This methodology was carried out at room temperature, using inexpensive and environmentally friendly iron salts as metallic source and under air atmosphere. The reaction showed to be tolerant to a range of substituents bonded into the aromatic ring of the diorganyl dichalcogenides as well as to alkyl groups directly bonded to the chalcogen atom. Alternatively, the cyclization reaction of 2-alkynylaryl esters with FeCl(3), in the absence of diorganyl dichalcogenide, gave the isochromenones without the chalcogen moiety in the structure. This approach proved to be highly regioselective, providing only six-membered ring products, once the possible five-membered products were not observed in any experiments.

Synthesis of Organochalcogen Propargyl Aryl Ethers and Their Application in the Electrophilic Cyclization Reaction: An Efficient Preparation of 3-Halo-4-Chalcogen-2H-Benzopyrans

We herein described the synthesis of various organochalcogen propargyl aryl ethers via reaction of lithium acetylide intermediate with electrophilic chalcogen (sulfur, selenium, tellurium) species. Various aryl and alkyl groups directly bonded to the chalcogen atom were used as electrophile. The results revealed that the reaction does not significantly depend on the electronic effects of substituents in the aromatic ring bonded to the chalcogen atom of the electrophilic chalcogen species. Additional versatility in this process was demonstrated with respect to a diverse array of functionality in the aromatic ring at propargyl aryl ethers. These propargyl aryl ethers, bearing the chalcogen group, underwent highly selective intramolecular cyclizations when treated with I(2) or ICl affording 3-iodo-4-chalcogen-2H-benzopyrans. The results demonstrated that the cyclization efficiency was significantly influenced by the steric effects of aromatic ring, since the cyclization reaction gave low yields with aromatic rings having a substituent at orto position than those having no substituent. The reactivity of 3-iodo-4-chalcogen-2H-benzopyrans was also studied. 4-Selenobutyl benzopyrans were treated under Neghishi cross-coupling conditions providing the corresponding 3-aryl benzopyran derivatives in good yields. In addition, using the copper catalyzed cross-coupling reactions with thiols, in the absence of any cocatalyst, we were able to introduce a thiol function in 3-iodo-benzopyran derivatives.

Hypolipidaemic activity of orally administered diphenyl diselenide in Triton WR-1339-induced hyperlipidaemia in mice

Objectives A significant association between the trace element selenium and hyper‐cholesterolaemia has been reported. This study was designed to investigate a potential hypolipidaemic effect of diphenyl diselenide ((PhSe)2) in Triton WR‐1339‐induced hyperlipidaemia in mice.

Iron(III) Chloride/Diorganyl Diselenides: A Tool for Intramolecular Cyclization of Alkynone O-Methyloximes

This report describes the synthesis of 4-organoselenylisoxazoles via FeCl(3)/RSeSeR-mediated intramolecular cyclization of alkynone O-methyloximes. The optimized conditions allowed the cyclization to proceed at room temperature under ambient atmosphere, and the reaction requires a short time to be completed. The reaction conditions tolerated neutral, electron-donating and electron-withdrawing groups present in both substrates, alkynone O-methyloximes and diorganyl diselenides. Treatment of 4-organoselenylisoxazoles with n-butyllithium, followed by trapping with electrophiles, furnished the functionalized isoxazoles in good yields. The obtained products also proved to be suitable substrates for the preparation of 4-bromoisoxazoles via Br/Se exchange reaction.