Iron(II)‐Catalyzed Direct Cyanation of Arenes with Aryl(cyano)iodonium Triflates

Abstract

A direct oxidative cyanation of arenes under Fe II catalysis with 3,5-di(trifluoromethyl)phenyl(cyano)iodonium triflate (DFCT) as the cyanating agent has been developed. The reaction is applicable to wide range of aromatic substrates, including polycyclic structures and heteroaromatic compounds.

Cobalt‐Catalyzed Electrophilic Cyanation of Arylzinc Halides with N‐Cyano‐N‐phenyl‐p‐methylbenzenesulfonamide (NCTS)

“…Nevertheless, the functionalization of unactivated CH bonds required a directing group and high temperature. In the same manner, a direct oxidative cyanation of arenes under Fe(II) catalysis using an excess of aryl(cyano)‐iodonium triflates as the cyanating agent has been successfully applied to a range of electron‐donating substituents on aromatic substrates 27. Although some elegant results were reported by CH activation, organometallic reagents remain useful to functionalize aryl halides without a directing group.…”

“…NCTS is ab ench-stable,e asy to handle and environmentally benign electrophilic cyanating agent. [27] Although some elegant results were reported by C À Ha ctivation,o rganometallic reagents remain useful to functionalizea ryl halides without ad irecting group.N evertheless,o rganozinc compounds known for their broad functional tolerance were rarely employed in cyanation. [21] Substituted arenes were cyanated in high yields andt hese methodst olerate both electronically rich/poorg roups at any place of the arene.…”

Palladium-Catalyzed Late-Stage Direct Arene Cyanation

“…[33][34][35][36][37] Alternatively, oxidative cyanation via a sequence of single electron transfer (SET) from electron-rich arenes with subsequent cyanide addition can be used effectively (Scheme 1B, Equation 2). [38][39][40][41] The groups of Kita 38 and Wang 39 independently reported hypervalent iodine(III)-mediated oxidative cyanation of electron-rich arenes. In 2017, McManus and Nicewicz reported a direct arene C-H cyanation reaction of electron-rich arenes via photoredox catalysis.…”

General and Practical Formation of Thiocyanates from Thiols

“…1‐Cyano‐3,3‐dimethyl‐1,2‐benziodoxole (CDBX, 11 ), also gave an excellent result (entry 8). The cyclic hypervalent iodine regents 10 and 11 were superior to iodonium salts such as 12 ,9j which led to the formation of disulfide 15 a as major product (entry 9).…”