Synthesis of Unsymmetrical Diorganyl Chalcogenides under Greener Conditions: Use of an Iodine/DMSO System, Solvent‐ and Metal‐Free Approach

Abstract

Herein, we report ag reener iodine-catalyzed protocoltoa ccess different typesofu nsymmetrical diorganyl chalcogenides.T his newa pproach works in the absenceo fs olvent and metal. Thed esired productsw ere obtained in good to excellent yields using one equivalento fa rylboronic acids,h alf an equivalento fv arious diorganyl dichalcogenides, iodine (10 mol%) as ac atalyst and 2equivalents of dimethyls ulfoxide (DMSO;a so xidant), with ar eaction time of 10 min under microwavei rradiation.

Copper-Catalyzed Synthesis of Unsymmetrical Diorganyl Chalcogenides (Te/Se/S) from Boronic Acids under Solvent-Free Conditions

“…Furthermore, CuO nanoparticles were less effective than copper iodide, affording the desired product in lower yield (entry 10). Considering our previous work [ 57 ], when 3% molecular iodine was used as catalyst, 3a was obtained in 69% yield (entry 11). The reaction in the absence of catalyst provided 3a in only trace amounts, which emphasizes the notable activity of CuI in this kind of transformation (entry 12).…”

“…Alternatively, we have recently reported suitable methods for the synthesis of unsymmetrical chalcogenides, using the iodine/DMSO system under microwave irradiation to generate, in situ, electrophilic species of chalcogenyl iodide (RYI) [ 57 ]. Similarly, Park and coworkers reported an ultrasound-assisted synthesis of diaryl ditellurides [ 58 ].…”

The Applications of Dimethyl Sulfoxide as Reagent in Organic Synthesis

“…Wei and co‐workers reported a selective synthesis of 2‐sulfanylphenols from non‐aromatic ketones 74. Braga and co‐workers reported an iodine‐catalyzed, metal‐free and solvent‐free method for the synthesis of a variety of unsymmetrical diorganyl chalcogenides under microwave irradiation 75. In these reactions DMSO can be used as the terminal oxidant to avoid the need for a transition metal.…”

Direct, Metal‐free C(sp2)−H Chalcogenation of Indoles and Imidazopyridines with Dichalcogenides Catalysed by KIO3

“…[12] Iodine catalysis represents ap romising powerful approach to organic synthesis becausei toffers advantages over transition-metal catalysis including greater atom economy,g reener and milder reaction conditions, andb roader substrate compatibility. [12] Iodine catalysis represents ap romising powerful approach to organic synthesis becausei toffers advantages over transition-metal catalysis including greater atom economy,g reener and milder reaction conditions, andb roader substrate compatibility.…”

“…In recent years, reactions catalysed by molecular iodine and iodines alts have emerged av ersatile tool in the cross-coupling reactionf or CÀCa nd CÀXb ond formation. [12] Iodine catalysis represents ap romising powerful approach to organic synthesis becausei toffers advantages over transition-metal catalysis including greater atom economy,g reener and milder reaction conditions, andb roader substrate compatibility. [13] Furthermore,m etal-and solvent-freer eaction conditionsh ave gained considerable attention from researchg roupsa nd are widely applied in the functionalization of the CÀHb ond, which represents an important contribution to the development and progress of sustainable chemistry.…”