Catalytic Cyanation Using CO2 and NH3

Abstract

Li and co-workers describe the catalytic cyanation of organic halides with CO 2 and NH 3 . In the presence of Cu 2 O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13 C-and/or 15 N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO 2 and NH 3 .

Recent developments in dehydration of primary amides to nitriles

“…27 Alternatively, alkyl/ aryl halides have also been catalytically converted to the corresponding amides using naturally abundant small molecules viz., CO 2 , NH 3 and urea. 28 In fact, syntheses of nitriles from nitrogen containing compounds such as amine, amides, etc., will be better alternatives than their non-nitrogen counterparts, as additional steps for the incorporation of the nitrogen functionality, involving the usage of stoichiometric reagents and generation of metal waste, can be avoided. Amides, apart from their easy availability, with a general formula of RCONR′ R″, are commonly found in numerous synthetic and natural products, besides their crucial role as basic building blocks of proteins in every form of life.…”

Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species

“…Here, it is interesting to stress that silyl isocyanate TMS-NCO is an appropriate CN source giving 74% yield of the desired product. The involvement of isocyanate intermediates has already been established in our previous work on the use of CO 2 /NH 3 as the cyanating reagent 47 .…”

“…Carbon dioxide is the most abundant carbon source, and is thus regarded as the most promising nontoxic C1 feedstock [41][42][43][44][45][46] . Recently, we developed the Cu-catalyzed reductive cyanation of aryl iodides with CO 2 /NH 3 as cyano (CN) source 47 . Herein, we report the reductive cyanation of organic chlorides using CO 2 / NH 3 or urea as either gaseous or solid forms of carbon and nitrogen, respectively (Fig.…”

Scalable direct N-methylation of drug-like amines using 12CO2/13CO2 by simple inorganic base catalysis

“…CH 3 CN was treated by a solvent purification system before use. 13 CO 2 were purchased from CIL. 1 H, 13 C, and 19 F NMR spectra were recorded on a Bruker Avance 500 or 400 spectrometer at ambient temperature.…”

“…1a) [8]. However, in spite of the tremendous progress in the field of direct chemical utilization of CO 2 in organic reactions [9][10][11][12][13][14][15], development of synthetic protocol with a general applicability to complex drug-like compounds ubiquitous in pharmaceutical industry remains a significant challenge [16].…”