Forging C‐SeCF₃ Bonds with Trifluoromethyl Tolueneselenosulfonate under Visible‐Light

Abstract

This account highlights some of our recent work on photoinduced trifluoromethylselenolation reactions. This research program relies primarily on the design of a new key shelf‐stable selenating reagent that can be involved in various radical processes In particular, we demonstrated that trifluoromethylselenolation of arenes, alkenes, alkynes as well as aliphatic organic building blocks can be readily achieved under visible‐light irradiation. Mechanistic investigations based on 19F NMR studies, EPR spectroscopy, cyclic voltammetry and luminescence studies allowed us to shed the light on the different proposed mechanisms in the designed methodologies. The applicative potential of these strategies was further demonstrated through the synthesis of bioactive analogue containing SeCF3 motif.

Progress in Photocatalyzed Trifluoromethylthiolation and Trifluoromethylselenolation Reactions

“…Direct trifluoromethylselenolation reactions have been confirmed to be the most convenient methods for the formation of the C–SeCF 3 bond with diverse SeCF 3 reagents (e.g., Hg(SeCF 3 ) 2 , CuSeCF 3 , AgSeCF 3 , [(bpy)CuSeCF 3 ] 2 , [Me 4 N][SeCF 3 ], ClSeCF 3 , CF 3 SeSeCF 3 , TsSeCF 3 , ArCH 2 Se(O)CF 3 , and the others). 6f 9h i 11 62 Even so, the synthetic strategies to introduce a SeCF 3 group into organic compounds are still underdeveloped in comparison with the analogous trifluoromethylthiolation. This section summarizes the advances in photoinduced trifluoromethylselenolation, which has attracted increasing attention in recent years.…”

“…TsSeCF 3 was synthesized from the reaction of the in situ formed ClSeCF 3 with toluenesulfinate, and has been used to implement radical trifluoromethylselenolations under visible-light irradiation. 9h i In 2018, the same research group reported the first photocatalytic trifluoromethylselenolation of arenediazonium salts 276 with TsSeCF 3 in the presence of an organic photocatalyst at room temperature under white LED irradiation, furnishing the trifluoromethylselenolated arenes 277 (Scheme 55 ). 71 The reaction did not require any additive and showed good functional group tolerance.…”

Recent Advances in Light-Induced Selenylation

“…44 In the past decade, trifluoromethyl tolueneselenosulfonate (TsSeCF 3 ) has been successfully employed as shelf stable reagent in trifluoromethylselenations taking place under photoredox catalyzed conditions. 45 Such derivative has been applied to the visible light driven synthesis of trifluoromethylselenolated arenes 6.1a−d and perfluoroalkylselenolated derivatives under metal-free conditions, by using Eosin Y as the photoredox catalyst (Scheme 6). The formation of the Ar−Se bond relies on the aryl radical addition onto TsSeCF 3 .…”

Synthetic Routes to Arylsulfonyl Fluorides

“…Interestingly, the reaction in the presence of halogen substituents gave the desired products in synthetically useful yields (15e-15h). To some extent, heterocyclic com- Very recently, we demonstrated that aryl sulfonyl fluorides could be obtained under visible-light metal-free procedures by using cyanoarenes as organophotocatalysts [35][36][37][38][39][40]. Indeed, the association of diazonium salts with DABSO in the presence or not of an external fluoride source (KHF 2 ) allows access to a wide variety of arylsulfonyl fluorides with moderate to very good yields (Scheme 12).…”