Nef isocyanide reaction

The Nef isocyanide reaction is an addition reaction that takes place between isocyanides and acyl chlorides to form imidoyl chloride products, a process first discovered by John Ulrich Nef.^[1]^[2]

The product imidoyl chloride can be hydrolyzed to give the amide, trapped with other nucleophiles, or undergo halide abstraction with silver salts to form an acyl nitrilium intermediate.^[3]

The reaction is of some theoretical interest, as kinetic measurements^[4] and DFT studies^[5] have indicated that the addition occurs in one step, without the intermediacy of a tetrahedral intermediate that is commonly proposed for carbonyl addition reactions.

References

^ Nef, J. U. (1892). "Ueber das zweiwerthige Kohlenstoffatom". Justus Liebig's Annalen der Chemie. 270 (3): 267–335. doi:10.1002/jlac.18922700302. ISSN 0075-4617.
^ Tron, Gian; El Kaïm, Laurent; La Spisa, Fabio (2014-03-05). "The Nef Reaction of Isocyanides". Synthesis. 46 (7): 829–841. doi:10.1055/s-0033-1338596. ISSN 0039-7881.
^ Westling, Mark; Smith, Richard; Livinghouse, Tom (April 1986). "A convergent approach to heterocycle synthesis via silver ion mediated .alpha.-ketoimidoyl halide-arene cyclizations. An application to the synthesis of the erythrinane skeleton". The Journal of Organic Chemistry. 51 (8): 1159–1165. doi:10.1021/jo00358a001. ISSN 0022-3263.
^ Ugi, Ivar; Fetzer, Uwe (April 1961). "Isonitrile, III. Die Addition von Carbonsäurechloriden an Isonitrile". Chemische Berichte (in German). 94 (4): 1116–1121. doi:10.1002/cber.19610940433. ISSN 0009-2940.
^ Chéron, Nicolas; El Kaïm, Laurent; Grimaud, Laurence; Fleurat-Lessard, Paul (2011-09-08). "A Density Functional Theory Study of the Nef-Isocyanide Reaction: Mechanism, Influence of Parameters and Scope". The Journal of Physical Chemistry A. 115 (35): 10106–10112. Bibcode:2011JPCA..11510106C. doi:10.1021/jp205909d. ISSN 1089-5639. PMID 21786773.

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[1] Nef, J. U. (1892). "Ueber das zweiwerthige Kohlenstoffatom". Justus Liebig's Annalen der Chemie. 270 (3): 267–335. doi:10.1002/jlac.18922700302. ISSN 0075-4617.

[2] Tron, Gian; El Kaïm, Laurent; La Spisa, Fabio (2014-03-05). "The Nef Reaction of Isocyanides". Synthesis. 46 (7): 829–841. doi:10.1055/s-0033-1338596. ISSN 0039-7881.

[3] Westling, Mark; Smith, Richard; Livinghouse, Tom (April 1986). "A convergent approach to heterocycle synthesis via silver ion mediated .alpha.-ketoimidoyl halide-arene cyclizations. An application to the synthesis of the erythrinane skeleton". The Journal of Organic Chemistry. 51 (8): 1159–1165. doi:10.1021/jo00358a001. ISSN 0022-3263.

[4] Ugi, Ivar; Fetzer, Uwe (April 1961). "Isonitrile, III. Die Addition von Carbonsäurechloriden an Isonitrile". Chemische Berichte (in German). 94 (4): 1116–1121. doi:10.1002/cber.19610940433. ISSN 0009-2940.

[5] Chéron, Nicolas; El Kaïm, Laurent; Grimaud, Laurence; Fleurat-Lessard, Paul (2011-09-08). "A Density Functional Theory Study of the Nef-Isocyanide Reaction: Mechanism, Influence of Parameters and Scope". The Journal of Physical Chemistry A. 115 (35): 10106–10112. Bibcode:2011JPCA..11510106C. doi:10.1021/jp205909d. ISSN 1089-5639. PMID 21786773.

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See also

References