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Synlett 2009(4): 681-682  
DOI: 10.1055/s-0028-1087716
SPOTLIGHT
© Georg Thieme Verlag Stuttgart ˙ New York

Methyl Cyanoformate (Mander’s Reagent)

Alex C. Bissember*
Research School of Chemistry, Institute of Advanced Studies, The Australian National University, Canberra, ACT 0200, Australia.
e-Mail: alexb@rsc.anu.edu.au;
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Publication History

Publication Date:
16 February 2009 (online)

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Introduction

Methyl cyanoformate, Mander’s reagent (Figure  [¹] ), is most commonly employed to effect the regiocontrolled synthesis of β-keto esters through the C-acylation of preformed lithium enolates. [¹] [²] It is superior to more traditional reagents such as acyl halides, anhydrides and carbon dioxide because these can also produce variable amounts of the corresponding O-acylated products. [³] In addition to its aforementioned electrophilic behaviour, methyl cyanoformate has also been employed as a dipolarophile [4] that reacts with an α-diazo-β-imido ester and, in the presence of polyoxotungstate, as a radical cyanating agent. [5] Its ­homologue ethyl cyanoformate also behaves as a dipolarophile [6] and has been used to form substituted tetrazoles. It has also been employed in the preparation of α-keto esters. [7]

Methyl cyanoformate is a commercially available, colourless liquid that is readily prepared in small quantities (up to 30 g) by treating methyl chloroformate with potassium cyanide in the presence of a phase transfer catalyst such as 18-crown-6 [8] or tetra-n-butylammonium bromide. [9]

Figure 1 Methyl Cyanoformate