Chemical evolution: from formamide to nucleobases and amino acids without the presence of catalyst

Enchev, Venelin; Angelov, Ivaylo; Dincheva, Ivayla; Stoyanova, Nina; Slavova, Sofia; Rangelov, Miroslav; Маркова, Н.

doi:10.1080/07391102.2020.1792986

Cited by 16 publications

(12 citation statements)

References 89 publications

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“…On the other hand, the structural properties of these HCN polymers (and hence their potential applications) as well as the single biomolecules and related organics found in them via chromatographic analysis all depend directly on the synthetic conditions used for their production [9][10][11][12][13] . However, despite the considerable developments in the area of microwave-assisted organic synthesis and polymerization in recent decades [14][15][16][17] , only one report describes the production of HCN-derived polymers from formamide using microwave radiation 18 .…”

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confidence: 99%

A dual perspective on the microwave-assisted synthesis of HCN polymers towards the chemical evolution and design of functional materials

Hortal

Pérez-Fernández

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et al. 2020

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In this paper, the first study on NH4CN polymerization induced by microwave radiation is described, where a singular kinetic behaviour, especially when this reaction is conducted in the absence of air, is found. As a result, a complex conjugated N-heterocyclic polymer system is obtained, whose properties are very different, and even improved according to morphological features, characterized by their X-ray diffraction patterns and scanning electron microscopy analysis, with respect to those produced under conventional thermal treatment. In addition, a wide variety of relevant bioorganics have been identified, such as amino acids, nucleobases, co-factors, etc., from the synthetized NH4CN polymers. These particular families of polymers are of high interest in the fields of astrobiology and prebiotic chemistry and, more recently, in the development of smart multifunctional materials. From an astrobiological perspective, microwave-driven syntheses may simulate hydrothermal environments, which are considered ideal niches for increasing organic molecular complexity, and eventually as scenarios for an origin of life. From an industrial point of view and for potential applications, a microwave irradiation process leads to a notable decrease in the reaction times, and tune the properties of these new series macromolecular systems. The characteristics found for these materials encourage the development of further systematic research on this alternative HCN polymerization.

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confidence: 99%

A dual perspective on the microwave-assisted synthesis of HCN polymers towards the chemical evolution and design of functional materials

Hortal

Pérez-Fernández

Fuente

et al. 2020

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“…As was mentioned in the Introduction, hypoxanthine was detected by Ferus et al [ 12 ] and by Enchev et al [ 13 ] by heating pure formamide at 160°C for 24 hours and at 140°C for 2 weeks, respectively. Here, we suggest a formamide/formimidic acid‐catalytic mechanism of hypoxanthine formation from urea, formic acid, and glycinamide.…”

Section: Discussionmentioning

confidence: 95%

“…In conclusion, the suggested reaction pathway for hypoxanthine formation from urea, formic acid, and glycinamide in pure formamide (Figure 2, blue line) is based on the possibility of the formation of these required raw materials by thermal decomposition of formamide. [ 13 ] It can be considered an alternative to the reaction pathway for the formation of hypoxanthine from 2‐aminomalononitrile and formamide presented in our previous paper. [ 19 ] In both reaction pathways, hypoxanthine is formed by an imidazole‐first mechanism, and the pyrimidine ring is then closed.…”

Section: Discussionmentioning

confidence: 99%

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Self‐catalytic mechanism of prebiotic reactions: II. From urea and glycinamide to hypoxanthine

Enchev

Slavova

2020

Int J of Quantum Chemistry

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Mechanisms of reactions for formylation of urea, leading to N,N′‐diformylurea, and for the dehydration of glycinamide and N,N′‐diformylurea, yielding hypoxanthine, are suggested. It is shown that these reactions are self‐catalyzed. The first is catalyzed by formic acid, while the second is catalyzed by N,N′‐diformylurea. The suggested reaction mechanism shows that the N3 and N9 atoms of hypoxanthine originate from urea in agreement with available 1H NMR experimental data by Lagoja and Herdewijn (Lagoja & Herdewijn, Chem. Biodiv. 2004, 1, 106). A complete reaction pathway of prebiotic reactions for formation of the hypoxanthine from urea, formic acid, and glycinamide in formamide, where formamide/formimidic acid plays the role of a proton‐carrying catalyst, is also suggested.

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“…Pioneering investigations by Robertson and Orgel have shown that the C5 position of uracil can easily bind formaldehyde, which enables formation of various C5-substituted uracil derivatives, among them that of thymine [ 20 ]. Nevertheless, with the exception of a recent report [ 21 ], in formamide medium, formation of thymine [ 22 ] has been observed exclusively in the presence of a catalysts [ 11 ] or in a radical chemistry [ 14 , 15 ]. For example, Saladino et al describe formation of thymine in the presence of TiO 2 [ 11 ].…”

Section: Introductionmentioning

confidence: 99%

Prebiotic Route to Thymine from Formamide—A Combined Experimental–Theoretical Study

et al. 2021

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Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers.

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Chemical evolution: from formamide to nucleobases and amino acids without the presence of catalyst

Cited by 16 publications

References 89 publications

A dual perspective on the microwave-assisted synthesis of HCN polymers towards the chemical evolution and design of functional materials

A dual perspective on the microwave-assisted synthesis of HCN polymers towards the chemical evolution and design of functional materials

Self‐catalytic mechanism of prebiotic reactions: II. From urea and glycinamide to hypoxanthine

Prebiotic Route to Thymine from Formamide—A Combined Experimental–Theoretical Study

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