A Cyanide‐Free Synthesis of Acylcyanides through Ru‐Catalyzed C(sp³)‐H‐Oxidation of Benzylic Nitriles

Abstract

A practical method for generation of acylcyanides devoid of any external cyanide sources is presented that relies on a mild Ru‐catalyzed selective C−H‐oxidation of benzylic nitriles. The starting materials are smoothly generated through condensation of the corresponding carboxylic acid amides using silanes. The obtained acylcyanides can be employed in a plethora of transformation as exemplified to some larger extend in the sequence of C−H‐oxidation‐Tischenko‐rearrangement for the generation of structurally diverse benzoyloxycyanohydrines.

Synthesis of N-Heteroarenemethyl Esters via C–C Bond Cleavage of Acyl Cyanides Under Transition Metal-Free Conditions

“…Recently, a simple and direct aerobic oxidative esterification reaction of arylacetonitriles with alcohols/phenols is achieved in the presence of a copper salt and molecular oxygen (Dong et al, 2021). On the other hand, Song and Plietker groups reported aerobic oxidative C-CN bond cleavage of arylacetonitriles leading to various esters with catalysis of Fe and Ru, respectively (Scheme 1C) (Kong et al, 2016;Eisele et al, 2019). In general, ester compounds could be achieved using acylcyanides as acylating agents.…”