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Issue 3, 2017
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Room temperature decarboxylative cyanation of carboxylic acids using photoredox catalysis and cyanobenziodoxolones: a divergent mechanism compared to alkynylation

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Abstract

The one-step conversion of aliphatic carboxylic acids to the corresponding nitriles has been accomplished via the merger of visible light mediated photoredox and cyanobenziodoxolones (CBX) reagents. The reaction proceeded in high yields with natural and non-natural α-amino and α-oxy acids, affording a broad scope of nitriles with excellent tolerance of the substituents in the α position. The direct cyanation of dipeptides and drug precursors was also achieved. The mechanism of the decarboxylative cyanation was investigated both computationally and experimentally and compared with the previously developed alkynylation reaction. Alkynylation was found to favor direct radical addition, whereas further oxidation by CBX to a carbocation and cyanide addition appeared more favorable for cyanation. A concerted mechanism is proposed for the reaction of radicals with EBX reagents, in contrast to the usually assumed addition elimination process.

Graphical abstract: Room temperature decarboxylative cyanation of carboxylic acids using photoredox catalysis and cyanobenziodoxolones: a divergent mechanism compared to alkynylation

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Publication details

The article was received on 04 Nov 2016, accepted on 13 Dec 2016 and first published on 22 Dec 2016


Article type: Edge Article
DOI: 10.1039/C6SC04907A
Citation: Chem. Sci., 2017,8, 1790-1800
  • Open access: Creative Commons BY-NC license
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    Room temperature decarboxylative cyanation of carboxylic acids using photoredox catalysis and cyanobenziodoxolones: a divergent mechanism compared to alkynylation

    F. Le Vaillant, M. D. Wodrich and J. Waser, Chem. Sci., 2017, 8, 1790
    DOI: 10.1039/C6SC04907A

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