Selectfluor^TM F-TEDA-BF₄ (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2]octane bis(tetrafluoroborate) is not only one of the most efficient and popular reagents for electrophilic fluorination, but as a strong oxidant is also a convenient mediator or catalyst of several “fluorine-free” functionalizations of organic compounds. Its applications as a mediator in transformations of oxidizable functional groups or gold-catalyzed C-C and C-heteroatom oxidative coupling reactions, a catalyst in formation of various heterocyclic rings, a reagent or catalyst of various functionalizations of electron-rich organic compounds (iodination, bromination, chlorination, nitration, thiocyanation, sulfenylation, alkylation, alkoxylation), a catalyst of one-pot-multi-component coupling reactions, a catalyst of regioselective ring opening of epoxides, a deprotection reagent for various protecting groups, and a mediator for stereoselective rearrangement processes of bicyclic compounds are reviewed and discussed.

Trituration of N-bromosuccinimide at room temperature with several liquid or solid 1,3-diketones and β-keto esters resulted in high yield conversion to the monobrominated derivatives, and a work-up procedure using only water to remove succinimide was employed. The entire process uses no organic solvent and is therefore more ecologically desirable.

Reactions of aryl alkyl ketones with methanol solution of elemental iodine and 1-fluoro-4-chloromethyl-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor™ F-TEDA-BF₄) result in the formation of corresponding α-iodo ketones, while switch over of the regioselectivity can be directed by using acetonitrile as the solvent and selective iodination of the aromatic site of target molecules is thus achieved.

Selective and efficient aerobic oxidative iodination of ketones in aqueous media was achieved by using molecular iodine as the source of iodine atoms, air as the terminal oxidant, sodium nitrite (NaNO₂) as the catalyst and H₂SO₄ as the activator of the overall catalytic process. The efficiency of the reaction, resulting in α-iodo ketones, was significantly improved in an aqueous solution of the anionic amphiphile sodium dodecyl sulfate (SDS), capable of self-assembly into micelle-based aggregates, thus forming a reactive micellar system. The regioselectivity of iodofunctionalization of aryl methyl ketones was regulated by the reaction medium used: in an aqueous micelle-based system the methyl group was iodinated, while in anhydrous MeCN aryl iodides were formed with high selectvity.