Solid‐State Direct Electrophilic Selenocyanation of (Hetero)Arenes using Mechanochemistry

Abstract

A mechanochemical direct selenocyanation of arenes/heterocyclic arenes with electrophilic selenocyanating reagents to access (hetero)aryl selenocyanates has been developed. This protocol provided an efficient strategy to access various aromatic selenocyanates in yields up to 99 % under ball‐milling reaction conditions within 60 minutes. Gram‐scale reaction and further transformations of the product were conducted to demonstrate the synthetic utilities of this method.

Paired Electrolysis Enabled Cyanation of Diaryl Diselenides with KSCN Leading to Aryl Selenocyanates

“…As a consequence, considerable efforts have been devoted to constructing such molecules, and a series of synthetic protocols have been developed [ 10 , 11 ]. The traditional methods can be divided into two categories according to the reaction substrates ( Scheme 1 a): (1) the reaction of phenylselenol or its derivative (PhSeH and PhSeCl) with a cyanating agent [ 12 , 13 ]; and (2) the reaction of various selenium-free aryl substrates with in-situ-generated selenocyanating agent (selenium powder/ trimethylsilyl cyanide, [ 14 , 15 ] selenium dioxide/malononitrile [ 16 ]) or the harmful potassium selenocyanate (KSeCN) [ 17 , 18 , 19 , 20 , 21 ]. Despite their achievements, the above-mentioned strategies generally require toxic and environmentally hazardous cyano sources; therefore, developing eco-friendly and more practical approaches for constructing such molecules from low-cost and non-toxic cyano sources are still highly desirable.…”