Aryl Sulfonium Salts for Site‐Selective Late‐Stage Trifluoromethylation

Abstract

Incorporation of the CF3 group into arenes has found increasing importance in drug discovery. Herein, we report the first photoredox‐catalyzed cross‐coupling of aryl thianthrenium salts with a copper‐based trifluoromethyl reagent, which enables a site‐selective late‐stage trifluoromethylation of arenes. The reaction proceeds with broad functional group tolerance, even for complex small molecules on gram scale. The method was further extended to produce pentafluoroethylated derivatives.

Regio‐ and Stereoselective Thianthrenation of Olefins To Access Versatile Alkenyl Electrophiles

“…We have recently published a site‐selective aromatic C(sp 2 )−H functionalization reaction of in situ activated thianthrene‐ S ‐oxides with trifluoroacetic anhydride . The formed aryl thianthrenium salts were used as aryl electrophiles to form challenging bonds such as aryl C−SCF 3 , C−CF 3 , C−N, C−O, and C−F bonds. An extension of aromatic substitution chemistry to olefins is generally not successful because olefins typically react with electrophiles by addition.…”

Catalytic Carbonylation and Carboxylation of Organosulfur Compounds via C−S Cleavage

“…This Minireview has discussed catalytic carbonylation and carboxylation of the CÀSb onds of organosulfur compounds with CO (or its equivalents) and CO 2 .B ecause of the inertness and catalyst-poisonous charactero fC ÀSb onds, such carbonylative transformations require harsh reaction conditions and/orf airly reactives ubstrates. Recently,s ulfonium salts are emerginga s satisfyingly general, sufficiently reactive,a nd readily accessible electrophilic coupling partnersm ainly by the contributions of Ritter, [19,24] Procter, [20a,d, 25] Zhang [26] and us. [18, 20c, 23, 27] As shown in Schemes 17-22, several carbonylative transformationso fh igh versatility have been also developed.…”

Oxidative Coupling Reactions of Arylboronic Acids and Fluoroform-Derived AgCF3

“…-62.3 (s, 3F); 13 C NMR (101 MHz, CDCl 3 ) δ: 134. 6,132.2,129.0,128.8,128.0,127.9,127.6 (q,J＝30 Hz),127.2,125.7 (q,J＝4.0 Hz), 124.3 (q, J＝271.0 Hz), 121.4 (q, J＝3.0 Hz).…”