Pd(OAc)2-catalyzed C–H activation of indoles: a facile synthesis of 3-cyanoindoles

Palladium-Catalyzed Norbornene-Mediated Tandem ortho-C–H-Amination/ipso-C–I-Cyanation of Iodoarenes: Regiospecific Synthesis of 2-Aminobenzonitrile

“…5-Iodo-1-methyl-1 H -indole ( 8a ) was found to react under the optimized reaction conditions, producing moderate yield of the corresponding product 1-methyl-4,6-dimorpholino-1 H -indole-5-carbonitrile ( 9aa ). We did not observe any C 3 -cyanation of indole under the reaction conditions, which is usually encountered in Pd-catalyzed cyanation …”

“…We did not observe any C 3 -cyanation of indole under the reaction conditions, which is usually encountered in Pd-catalyzed cyanation. 15 Interestingly, meta-CF 3 -substituted iodoarene showed excellent regioselectivity toward C−H-amination/C−I-cyanation under the reaction conditions (Scheme 6). Here, amination occurred exclusively at the position para to the −CF 3 group.…”

Aerobic Oxidative Functionalization of Indoles

“…Particularly, for the 2substituted indole substrates DMSO instead of DMF was used and base was removed from the catalytic systems (OAc) 2 and 40 mol % CuBr 2 under air conditions, with a wide range of the corresponding 3-cyanoindoles produced in good yields with high regioselectivity. [68] In 2011, Cheng and co-workers developed palladium-catalyzed cyanation of indole CÀ H bonds with the combination of NH 4 HCO 3 and DMSO as the safe cyanide source (Scheme 26). [69] Notably, in this aerobic cyanation, stoichiometric amounts of Cu(OAc) 2 (1.1 equiv.)…”

Advances in C–CN Bond Formation via C–H Bond Activation

“…On the basis of Cheng’s work, Reddy described the Pd­(II)-catalyzed cyanation of indoles via C–H bond activation employing CuCN as the cyano-group source (Scheme ). The reaction tolerated various free indoles with both electron-withdrawing and electron-donating substituents as well as N-substituted indoles to give the corresponding 3-cyanated derivatives in good yields with high regioselectivity.…”