Recent advances and perspectives in ruthenium-catalyzed cyanation reactions

Abstract

The cyanation reaction has achieved rapid progress in recent times. The ability to exhibit multiple oxidation states increased the demand of ruthenium in the field of catalysis. These cyanation reactions have wide application in pharmacological and biological fields. This review gives an overview of the ruthenium-catalyzed cyanation reactions covering literature up to 2021.

Reaction mechanism – explored with the unified reaction valley approach

“…207–209 The first transition metal-catalyzed cyanation reaction was reported in 1919 using Cu as the catalyst. 210 Rhodium entered the scene with the discovery of Wilkonson's catalyst [RhCl(PPh 3 ) 3 ] 211,212 which was instrumental for the fundamental understanding of metal–H interactions and hydrogen activation leading to the emerging field of designing catalysts for efficient support of both C–C bond formation and C–H cleavage via C–H bond activation, 213–220 and more broadly, contributing to two essential tasks in organic synthesis, namely C–C bond formation 221–224 and C–H bond activation. 225–228…”

“…[207][208][209] The first transition metal-catalyzed cyanation reaction was reported in 1919 using Cu as the catalyst. 210 Rhodium entered the scene with the discovery of Wilkonson's catalyst [RhCl(PPh 3 ) 3 ] 211,212 which was instrumental for the fundamental understanding of metal-H interactions and hydrogen activation leading to the This journal is © The Royal Society of Chemistry 2023 emerging field of designing catalysts for efficient support of both C-C bond formation and C-H cleavage via C-H bond activation, [213][214][215][216][217][218][219][220] and more broadly, contributing to two essential tasks in organic synthesis, namely C-C bond formation [221][222][223][224] and C-H bond activation. [225][226][227][228] In the following we discuss the URVA results for a model reaction describing the Rh-catalyzed formation of acetonitrile starting from an (Z 5 -C 5 H 5 )Rh(PH 3 )(CH 3 )(CN) complex, a simplified version of the (Z 5 -C 5 Me 5 )Rh(PMe 3 )(CH 3 )(CN) catalyst suggested by Evans.…”

Electrochemical synthesis of CN-substituted imidazo[1,5-a]pyridines via a cascade process using NH4SCN as both an electrolyte and a non-trivial cyanating agent

“…The cyano group is one of the versatile synthons in organic chemistry, and much effort has been directed towards developing cyanation methods. [1][2][3][4][5][6][7][8][9] Recently, in view of the toxicity of metal cyanides, "non-metal" organic [CN] sources such as acetonitrile, tosyl cyanide (TsCN), 2,2′-azobis-(isobutyronitrile) (AIBN), 10,11 N-cyanosuccinimide, and N-cyano-N-phenyl-ptoluenesulfonamide (NCTS) 12 as well as combined [CN] sources ([NH 3 ] with DMF or DMSO) have become attractive (Scheme 1). [13][14][15][16][17] Thiocyanate salt oxidation has been shown to produce cyanide ions under the action of various chemical oxidants.…”