AIBN as an Electrophilic Reagent for Cyano Group Transfer

Abstract

AIBN is a convenient electrophilic cyanation reagent for transforming ArLi into ArCN under mild conditions. The addition/ fragmentation cascade is controlled by Li•••N chelation in which AIBN nitrogens assist in the nearly barrierless fragmentation into the desired ArCN product. Acidic C−H bonds in the fragmented byproduct partially consume ArLi by protonation. Density functional theory calculations and isotopic labeling probe the mechanism and explain the switch to substituted hydrazones in reactions with BuLi.

Tethering Three Radical Cascades for Controlled Termination of Radical Alkyne peri-Annulations: Making Phenalenyl Ketones without Oxidants

“…Note that equivalent of AIBN should generate two equivalents of C-centered radicals. The need to use a large amount of AIBN suggests the inefficiency of the radical propagation, which is consistent with the multiple roles of AIBN, which can be involved in more than one step of the radical cascade (see the Supporting Information). Oxidative workup with DDQ did not increase the yield (Table , entry 8).…”

Visible‐Light‐Mediated Photocatalyst‐Free Hydroacylation of Azodicarboxylic Acid Derivatives with 4‐Acyl‐1,4‐dihydropyridines

“…The 1,1'‐(azodicarbonyl)‐dipiperidine (4j), azodicarboxylic dimor pholide (4k—4t) and diazene‐1,2‐diylbis((4‐ethylpiperazin‐1‐yl)methanone) (4u) were all amenable substrates for this protocol. Interestingly, the radical initiator azobisisobutyronitrile (AIBN), [ 16 ] in this case, functioned as the radical acceptor to give 4v in 75% yield, further showcasing the mildness of our protocol. Moreover, the RCA of less‐explored unsymmetrical azo‐compound such as ethyl ( E )‐2‐phenyldiazene‐1‐carboxylate was accomplished under identical conditions, leading to 4w and 4x in 56% and 53% yield, respectively.…”

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.…”