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

Intramolecular Aminocyanation of Alkenes by NCN Bond Cleavage

“…Recently, N-cyano-N-phenyl-p-toluene sulfonamide (NCTS) has been employed as a bench-stable and less-toxic cyanation reagent in metal-catalyzed cross-coupling [21] and arene CÀH cyanations, [22] thus implying a metal-mediated NÀCN cleavage process. Meanwhile, Lewis acid cocatalysts, particularly BPh 3 , have proven effective at accelerating metal-catalyzed carbocyanation [23] and oxycyanation [10] of alkenes.…”

Copper-catalyzed cyanation of aryl iodides with α-cyanoacetates via C–CN bond activation

“…Considering the fact that oxygen is crucial to this reaction (refer to discussions related to Table 1), it is possible that the CH 2 CO 2 Et part might be oxidized by oxygen to get oxalate derivatives, which may easily sublime from the reaction solution 15 or further decompose to release CO 2 under the reaction conditions. 20 Additional evidence supporting this hypothesis is that the reaction mixture shown in Table 1 Scheme 2 Plausible mechanism for this cyanation reaction As a result, a plausible mechanism profile is suggested as shown in Scheme 2 for this copper-catalyzed cyanation reaction.…”

“…1 Aryl nitriles are also synthetic intermediates for an array of valuable functionalized compounds, e.g., amines, imines, ketones and N-heterocycles, taking advantage of the 15 versatile conversion of cyano functional group. 2 Therefore, the search for efficient aromatic cyanation reactions has been a longstanding interest.…”

“…5 In addition, more 40 complicated strategies for generating CN group from combined sources have been reported to achieve aromatic cyanation reactions, e.g., DMF + NH 3 , 12 DMF + NH 4 I, 13 DMF + NH 4 HCO 3 14 and etc. 15 In recent years, transition metal-mediated C-C bond activation 45 reactions have emerged as a promising tool for organic synthesis due to the prevalence of C-C bond in organic molecules. 16 Among them, the activation of C-CN bond of nitriles by a transition metal complex (typically a Ni(0) or Rh(I) complex) has been well studied to yield TM-CN (TM denotes a transition metal 50 complex) intermediates.…”

“…The reactivity of aryl halides follows an apparent trend of ArI > ArBr > ArCl. This strongly implies that aryl halide activation should be rate-limiting under the reaction conditions 15 for this reaction. Further efforts are still required for these challenging substrates.…”