Abstract:MARTINO PAVENTI and JOHN T. EDWARD. Can. J. Chem. 65, 282 (1987). The conversion of aldehydes into a-aminonitriles and thence into imidazolidin-4-thiones has been studied. Hydrolysis of the appropriate imidazolidin-4-thiones gave thioamides of nine naturally occurring a-amino acids. The possible pre-biotic significance of these compounds is discussed.MARTINO PAVENTI et JOHN T. EDWARD. Can. J. Chem. 65,282 (1987). On a CtudiC la transformation des aldChydes en a-amino-nitriles et Cventuellement en imidazolidine… Show more
“…[53][54][55][56][57] This reaction course was explained by cyclo-condensation of the corresponding ketone released from α-aminonitrile together with the formed α-aminothioamide (Scheme 9).…”
Section: Methodsmentioning
confidence: 99%
“…[53][54][55][56][57] A particular case of hydrolysis of 2,2,5,5-tetramethylimidazoline-4-thione gave 2-amino-2-methylthiopropanamide (Scheme 11). …”
This review article summarizes recent developments and trends in the application of 2-amino-2-alkyl(aryl)propanenitriles as precursors for the syntheses of heterocyclic systems such as imidazole derivatives, oxazoles, isothiazoles and 1,3,2-diazaphospholidines. Also described are less usual examples of applications in which they and their analogies react as monofunctional precursors, or where they have been used as sources of a nitrile carbon atom, or as catalysts or initiators. Their chemical and/or biological properties and potential applications are discussed, along with those of the derived heterocycles.
“…[53][54][55][56][57] This reaction course was explained by cyclo-condensation of the corresponding ketone released from α-aminonitrile together with the formed α-aminothioamide (Scheme 9).…”
Section: Methodsmentioning
confidence: 99%
“…[53][54][55][56][57] A particular case of hydrolysis of 2,2,5,5-tetramethylimidazoline-4-thione gave 2-amino-2-methylthiopropanamide (Scheme 11). …”
This review article summarizes recent developments and trends in the application of 2-amino-2-alkyl(aryl)propanenitriles as precursors for the syntheses of heterocyclic systems such as imidazole derivatives, oxazoles, isothiazoles and 1,3,2-diazaphospholidines. Also described are less usual examples of applications in which they and their analogies react as monofunctional precursors, or where they have been used as sources of a nitrile carbon atom, or as catalysts or initiators. Their chemical and/or biological properties and potential applications are discussed, along with those of the derived heterocycles.
“…This would be expected to yield the imidazolidine-4-thione 10 by the mechanism shown in Scheme 2 (15). In fact, this compound was obtained, but in small yield, along with the compounds 11 and 13 (15).…”
mentioning
confidence: 93%
“…This would be expected to yield the imidazolidine-4-thione 10 by the mechanism shown in Scheme 2 (15). In fact, this compound was obtained, but in small yield, along with the compounds 11 and 13 (15). Evidently steric hindrance at the cyclization step leading to 10 is sufficient to allow the competing hydrolysis of the intermediate to yield 11, and steric hindrance at an earlier stage causes 2 to react so slowly that the competing breakdown of 2 to adamantanone, NH3, and HCN (13) can result in the formation of significant amounts of 12 and thence of 13.…”
Attempts to hydrolyse the nitrile group of 2-aminoadamantane-2-carbonitrile by mineral acid or alkali have been unsuccessful. However, treatment of the aminonitrile with benzaldehyde in alkaline solution gives the benzal derivative of the α-aminoamide, readily hydrolysed to the α-aminoamide. Alternatively, benzoylation of the amino group followed by acid hydrolysis gives successively the α-benzamido acid and the α-amino acid. Possible mechanisms for these facilitated hydrolyses are advanced.
“…The implication of HCN in both amino acid and nucleotide synthesis strongly suggests the importance of cyanide chemistry at the origins of life 2 . However, Strecker synthesis is highly pH dependant and is reversible under sufficiently acidic or alkaline conditions 3 . Moreover, if a successful synthesis of aminonitrile 2 (or amino acid 3) can be achieved under prebiotic constraints, subsequent activation is required for peptide synthesis.…”
The central and conserved role of peptides in extant biology suggests that they played an important role during the origins of life. Strecker amino acid synthesis appears to be prebiotic, but the high pK aH of ammonia (pK aH = 9.2) necessitates high pH reaction conditions to realise efficient synthesis, which places difficult environmental constraints on prebiotic amino acid synthesis. Here we demonstrate that diamidophosphate reacts efficiently with simple aldehydes and hydrogen cyanide in water at neutral pH to afford N-phosphoro-aminonitriles. N-Phosphoro-aminonitrile synthesis is highly selective for aldehydes; ketones give poor conversion. N-Phosphoro-aminonitriles react with hydrogen sulfide at neutral pH to furnish aminothioamides. The high yield (73%-Quant.) of N-phosphoro-aminonitriles at neutral pH, and their selective transformations, may provide new insights into prebiotic amino acid synthesis and activation.
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