Nucleophilic displacements on sulfonyl cyanides

A General Rhodium‐Catalyzed Cyanation of Aryl and Alkenyl Boronic Acids

“…Furthermore, electronically different aryl boronic acids reacted smoothly and afforded the corresponding nitriles in good yield (Table 3, entries 2-4 and 9-11). Moreover, more challenging functionalized aryl boronic acids are also compatible with the present cyanation conditions ( Table 3, entries [11][12][13][14]. For example, 5-cyano-N-methylindole was formed in 76 % yield from the commercially available indolylboronic acid.…”

“…[11] Furthermore, electrophilic cyanation of organolithium, organomagnesium, and organozinc reagents are known. [12] Most recently, we disclosed a general cyanation of Grignard reagents through the use of N-cyanobenzimidazole (4). [13] Despite all these studies, the cyanation of more stable and readily available organometallic reagents such as organoboron derivatives has only been rarely studied.…”

The Construction of X–CN (X=N, S, O) Bonds

“…[54] In addition,M artin developed the synthesis of cyanate esters using phenyl thioxochloroformate and NaN 3 in 1964 [Eq. [56] However, no major advance has emerged recently.A saresult, further studies are needed to develop as afea nd efficient O-cyanation. [55] Tosyl cyanide bearing activated an cyano group was employed as an alternative cyano source by van Leusen andJ agt to produce cyanate esters[ Eq.…”

p-Toluenesulfonyl Cyanide

“…Tosyl cyanide acts as an electrophilic cyanating agent in reactions with many nucleophiles including phenoxides, Grignard reagents, amines, and thiols. 7 Tosyl cyanide proved to be a much more effective reagent for the cyanations of ketone enolates than either Cyanogen Bromide or phenyl cyanate, although the yields were low with methyl ketones. 8 Reaction of vinylcuprates with tosyl cyanide provided a stereospecific synthesis of 2-alkenenitriles (yields >90%), although cyanogen chloride could also be used.…”