Synthesis of cyanoformamides from primary amines and carbon dioxide under mild conditions. Synthesis of ceratinamine

Abstract

Treatment of primary amines with tetramethylphenylguanidine (PhTMG) and a cyanophosphonate at -10 degrees Celsius under an atmosphere of carbon dioxide provides cyanoformamides in very high to excellent yields. The reaction proceeds efficiently within a short time. By-products were not detected in most runs and epimerization was not found when optically pure alpha-aminoesters were used as substrates. As an example, the reaction was applied to the synthesis of the marine natural product ceratinamine.

Solvent‐Free Synthesis of Cyanoformamides from Carbamoyl Imidazoles

“…s, 1 H min ), 4.60 (d, J = 6.5 Hz, 2 H min ), 4.43 (d, J = 5.7 Hz, 2 H maj ), 3.82 (s, 3 H min ), 3.81 (s, 3 H maj ) ppm. Spectral data were consistent with those reported …”

“…For example, traditional syntheses of cyanoformamides from an amine and carbonyl cyanide, or from carbamoyl chlorides and a cyanide ion, require the use of toxic and potentially explosive reagents . More recent advances include the reaction of primary amines with carbon dioxide followed by a cyanophosphonate; the reaction of 1‐acyl‐1‐carbamoyl oximes with POCl 3 , and; the cyanocarbonylation of amines with iso ‐nitroso‐Meldrum's acid . All of these reactions require the use of exotic and commercially unavailable reagents.…”

Green Synthesis of 1,3‐Dibenzylimidazolidine‐2,4,5‐triones by Oxidation of Hexabenzylhexaazaisowurtzitanes

“…Spectral data of the unsubstituted product (Table , entry 1) is fully compatible with the previously reported ones . The other derivatives of 1,3‐dibenzylimidazolidine‐2,4,5‐trione, synthesized by this procedure, were fully characterized by their 1 H NMR, 13 C NMR, IR, and Mass spectra (see vide infra and supplementary document).…”

Sulfated phenolic compounds from Limonium caspium: Isolation, structural elucidation, and biological evaluation

“…In this study the ethanolic extract derived from the aerial parts of L. caspium was subjected to multiple chromatographic fractionations over silica gel yielding a series of myricetin derivatives including two new dihydromyricetins: (2 S ,3 S )-5-methyldihydromyricetin ( 1 ), and ( 2 S,3 S )-5-methyldihydromyricetin-3′- O -sulfate ( 2 ), six previously reported myricetins; dihydromyricetin ( 4 ) [9], dihydromyricetin-3′- O -sulfate ( 5 ) [11], myricetin-3′- O -sulfate ( 6 ) [11], 5-methylmyricetin ( 7 ), myricetin ( 8 ) [10], myricetin-3-β-glucoside ( 9 ) [12], and a new β-D-glucopyranoside, 3-methyl, but-3-en-1-yl 4-O-α-L-rhamnopyranosyl ( 3 ), phloridzin ( 10 ) [13], and tyramine ( 11 ) [14] (Fig. 1).…”