Electrochemical alkene azidocyanation via 1,4-nitrile migration

Abstract

An organic oxidant free electrochemical method for the azidocyanation of alkenes via 1,4-nitrile migration has been developed.

Reshuffle Bonds by Ball Milling: A Mechanochemical Protocol for Charge-Accelerated Aza-Claisen Rearrangements

“…instead of acetyl chloride increased the yield slightly (17.0 mg, 0.10 mmol, 20%). The NMR data closely match the ones previously reported in the literature [ 154 ]. R f = 0.33 (pentane:EtOAc 1:1), stains with KMnO 4 .…”

Catalytic Radical‐Polar Crossover Non‐Classical Semipinacol Rearrangements: The Sustainable Approach

“…In this direction, an electrochemical azidocyanation‐semipinacol rearrangement cascade was reported by Morrill group for the synthesis of variously substituted ketones (Scheme 38). [66] The method included the reaction of cyanohydrins 38 a with sodium azide and Mn‐salt in an electrolytic cell to give cyano‐ketones 38 b in good yield. The suggested mechanism included the formation of azide radical, which upon alkenation generated alkyl radical Int‐38 c .…”

“…In this direction, an electrochemical azidocyanation-semipinacol rearrangement cascade was reported by Morrill group for the synthesis of variously substituted ketones (Scheme 38). [66] The method included the reaction of cyanohydrins 38 a with sodium azide and Mn-salt in an electrolytic cell to give cyano- An unique strategy describing in situ generation alkoxy sulfonyl radical in an electrolytic cell from the combination of alcohol and sodium metabisulfite and its subsequent participation in a cascade semipinacol rearrangment was delineated by Ye et al for the synthesis of various ketone. This particular unusual combination not only could open a completely new way to the generation of such unexplored radicals, but also offered rapid access to synthetically challenged and valuable intermediates or synthons.…”

Electrochemical Difunctionalization of Alkenes

“…Delightedly, this electrochemical functionality migration strategy was applicable to the azidocyanation of alkenes through 1,4-nitrile migration (Scheme 40 ). 28 Morrill and co-workers used a manganese(II) salt to promote the electrochemical azidocyanation of various alkenes containing cyanohydrins under organic-oxidant-free conditions, providing access to a broad range of synthetically useful 1,2-azidonitriles (28 examples). In this protocol, the steric hindrance around the aromatic ring has no obvious effect on the reaction when cyanohydrin is used as the starting material, and various substituents can be introduced into the aromatic ring.…”