Nef isocyanide reaction

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The Nef isocyanide reaction is a name reaction in organic chemistry , which was first published in 1892 by the American chemist John Ulric Nef (1862–1915). The Nef isocyanide reaction is an addition reaction and should not be confused with the more popular Nef reaction .

Reaction scheme

The Nef isocyanide reaction describes the reaction of a carboxylic acid chloride ( 1 ) with an isonitrile ( 2 ) with the formation of carboxylic acid chloride imide ( 3 ):

Reaction schemes for the Nef isocyanide reaction

The carboxylic acid chloride imide ( 3 ) can be hydrolyzed to an amide , other nucleophilicity trapped, or halide abstraction with silver salts to form an acyl nitrilium intermediate.

application

The Nef isocyanide reaction is of theoretical interest because kinetic measurements and DFT studies have shown that the addition occurs in one step without the interposition of a tetrahedral intermediate that is commonly proposed for carbonyl addition reactions .

See also

Individual evidence

  1. ↑ JU Nef: About the divalent carbon atom . In: Justus Liebig's Annals of Chemistry . 270, No. 3, September, pp. 267-335. doi : 10.1002 / jlac.18922700302 .
  2. ^ A b Gian Tron: The Nef Reaction of Isocyanides . In: Synthesis . 46, No. 7, September, pp. 829-841. doi : 10.1055 / s-0033-1338596 .
  3. ↑ Mark Westling: A convergent approach to heterocycle synthesis via silver ion mediated .alpha.-ketoimidoyl halide-arene cyclizations. An application to the synthesis of the erythrinane skeleton . In: The Journal of Organic Chemistry . 51, No. 8, September, pp. 1159-1165. doi : 10.1021 / jo00358a001 .
  4. ^ Ivar Ugi: Isonitrile, III. The addition of carboxylic acid chlorides to isonitriles . In: Chemical Reports . 94, No. 4, September, pp. 1116-1121. doi : 10.1002 / cber.19610940433 .
  5. ↑ Nicolas Chéron: A Density Functional Theory Study of the Nef-Isocyanide Reaction: Mechanism, Influence of Parameters and Scope . In: Journal of Physical Chemistry A . 115, No. 35, September, pp. 10106-10112. doi : 10.1021 / jp205909d . PMID 21786773 .