The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles

Abstract

The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of N,N-disubstituted aminomalononitriles.

Iodine-DMSO mediated conversion of N-arylcyanothioformamides to N-arylcyanoformamides and the unexpected formation of 2-cyanobenzothiazoles

“…Recently, other more direct synthetic methods have been developed (Scheme 2). 23–29 For instance, Muñoz reported that the reaction of primary amines with tetramethylphenylguanidine and cyanophosphonates at −10 °C under an atmosphere of CO 2 furnishes cyanoformamides in good yields. 23 Dong and co-workers 24 employed phosphoryltrichloride (POCl 3 ) to convert 1-acyl-1-carbamoyl oximes to cyanoformamides, while concurrently Wu and co-workers 25 reported an eco-friendly method for the conversion of 2-oxoaldehydes into cyanoformamides using iodosobenzene diacetate (IBD) as oxidant.…”

“… 26 At the same time, Schwartz's group described solvent-free access to secondary and tertiary cyanoformamides from TMSCN and carbamoyl imidazoles. 27 Recently, cyanoformamides were prepared from N , N -disubstituted aminomalononitriles 28 with CsF as the promoter and in another study, 4,5-dioxo-imidazolinium cation activation of 1-acyl-1-carbamoyl oximes was used. 29 Electrochemical synthesis of cyanoformamides was also reported starting from trichloroacetonitrile and secondary amines mediated by heptamethyl cobyrinate, a B 12 derivative.…”

Progression on Oxidative Decyanation Approaches from Secondary Nitriles to Ketones and α‐Aminonitriles to Amides

“…Wang and co‐workers (2019) reported an efficient method for synthesizing formamides [39] 63 by CsF‐promoted oxidative decyanation of 2‐dialkylamino malononitriles 62 (Scheme 33). An alternative finding for the preparation of cyano formamides was conventionally prepared from primary and secondary amines.…”

4,5-Dioxo-imidazolinium Cation Activation of 1-Acyl-1-carbamoyl Oximes: Access to Cyanoformamides Using Dichloroimidazolidinedione

“…Yet, the use of highly toxic and structurally complex reagents hampered their synthetic applications. Until recently, sporadic examples of alternative approaches to cyanoformamide formation were reported . Although effective, most of these protocols called for elevated temperatures (60–140 °C) ,− and long reaction times , or suffered from limited product scope excluding secondary cyanoformamides. ,, It is worthy of note that Dong and co-workers reported a new pathway for the synthesis of cyanoformamides from readily accessible 1-acyl-1-carbamoyl oximes mediated by phosphoryltrichloride (POCl 3 ) .…”