Reagents and Synthetic Methods 30. Practical and Improved Method for Formylating Amino Compounds by Means of Formic Acid-Dimethylformamide System

Aizpurua, J. M.; Palomo, Claudio

doi:10.1080/00397918308063704

Cited by 10 publications

(5 citation statements)

References 17 publications

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“…Based on the seminal Miller experiment, [21] 9 is possibly formed through a Strecker condensation between hydrogen cyanide, formaldehyde and ammonia, which are generated in situ by formamide degradation in the phosphate microenvironment, followed by a N-formylation step in the presence of excess formamide. [22,23] The synthesis of carbodiimide (10), which is an important agent for the condensation of amino acids into peptides, [24] could be due to the formation of 9 from in situ generated glycine (not isolated). This suggests a role for the formamide-phosphate system in prebiotic synthesis of peptides.…”

Section: Resultsmentioning

confidence: 99%

Origin of Informational Polymers: The Concurrent Roles of Formamide and Phosphates

et al. 2006

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Formamide chemistry provides a unitary system by gathering all of the precursors needed to synthesise pregenetic informational polymers in a single milieu. This is not observed with HCN chemistry. With common catalysts, formamide affords all of the precursor nucleobases, photochemically condenses into acyclonucleosides, favours transphosphorylation and enhances micellar aggregation of surfactants. Also, formamide provides a set of physicochemical conditions that thermodynamically favour the polymeric state of nucleotides over the monomers. In the origin-of-informational-polymers scenario, formamide acts in every step, the least characterised being the set of its reactions with phosphates. On this matter, we report two complementary sets of results: 1) the synthesis of prebiotic precursors from formamide, which are catalysed by soluble and mineral phosphates-we observed the formation of rich mixtures that include uracil, 9H-purine, cytosine, dihydrouracil, hypoxanthine, adenosine, urea, parabanic acid, the amino acid N-formylglycine and the peptide-condensing agent carbodiimide; and 2) the protection of ribo- and deoxyribophosphoester bonds by phosphates. The relevance of these effects with respect to the origin of informational polymers is discussed.

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Section: Resultsmentioning

confidence: 99%

Origin of Informational Polymers: The Concurrent Roles of Formamide and Phosphates

et al. 2006

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“…Initially, we investigated the behavior of aminonitriles 1 (AA-CN, AA = amino acid) in formamide. Unsurprisingly, given synthetic formylation procedures, , glycine nitrile (Gly-CN 1a ), alanine nitrile (Ala-CN 1b ), and valine nitrile (Val-CN 1c ) were readily N -formylated in good yield by heating their acid salts in formamide in an open vessel exposed to air and moisture (Table , entries 1–3; Graph S1; and Figures S1–S9). Gly-CN 1a formylated at an appreciable rate at room temperature (RT), while Ala-CN 1b and Val-CN 1c required heating to 80 °C to achieve high conversion after16 h. Formylated aminonitriles (FoAA-CN 2 ) FoGly-CN 2a , FoAla-CN 2b , and FoVal-CN 2c were stable when heated to 100 °C in formamide, without any additional products being observed.…”

Section: Resultsmentioning

confidence: 99%

Prebiotic Synthesis of N-Formylaminonitriles and Derivatives in Formamide

et al. 2023

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Amino acids and their derivatives were probably instrumental in the transition of prebiotic chemistry to early biology. Accordingly, amino acid formation under prebiotic conditions has been intensively investigated. Unsurprisingly, most of these studies have taken place with water as the solvent. Herein, we describe an investigation into the formation and subsequent reactions of aminonitriles and their formylated derivatives in formamide. We find that N-formylaminonitriles form readily from aldehydes and cyanide in formamide, even in the absence of added ammonia, suggesting a potentially prebiotic source of amino acid derivatives. Alkaline processing of N-formylaminonitriles proceeds with hydration at the nitrile group faster than deformylation, protecting aminonitrile derivatives from reversion of the Strecker condensation equilibrium during hydration/hydrolysis and furnishing mixtures of N-formylated and unformylated amino acid derivatives. Furthermore, the facile synthesis of N-formyldehydroalanine nitrile is observed in formamide from glycolaldehyde and cyanide without intervention. Dehydroalanine derivatives have been proposed as important compounds for prebiotic peptide synthesis, and we demonstrate both a synthesis suggesting that they are potentially plausible components of a prebiotic inventory, and reactions showing their utility as abiotic precursors to a range of compounds of prebiological interest.

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“…On the basis of the Eschenmoser hypothesis (Eschenmoser 2007) concerning the relationship between HCN and the constituents of the reductive citric acid cycle, we suggest that compounds 10-13 were produced by a common reaction pathway involving the hydrolysis of the nitrile group to form reactive intermediates, such as the HCN-dimer and the HCN-tetramer. N-formylglycine 14 was previously synthesized from formamide and mineral phosphates (Saladino et al 2006a,b) probably through a Strecker condensation (Miller 1953) between HCN, formaldehyde and ammonia, possibly derived from formamide (Saladino et al 2007), followed by formylation of the amino moiety by formamide (Aizpurua and Palomo 1983). Note that this latter reactive step is a simple model for the formation of the peptide bond.…”

Section: Reaction Mechanismmentioning

confidence: 97%

Catalytic effects of Murchison Material: Prebiotic Synthesis and Degradation of RNA Precursors

Saladino

Crestini

Cossetti

et al. 2011

Orig Life Evol Biosph

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Mineral components of the Murchison meteorite were investigated in terms of potential catalytic effects on synthetic and hydrolytic reactions related to ribonucleic acid. We found that the mineral surfaces catalyzed condensation reactions of formamide to form carboxylic acids, amino acids, nucleobases and sugar precursors. These results suggest that formamide condensation reactions in the parent bodies of carbonaceous meteorites could give rise to multiple organic compounds thought to be required for the emergence of life. Previous studies have demonstrated similar catalytic effects for mineral assemblies likely to have been present in the early Earth environment. The minerals had little or no effect in promoting hydrolysis of RNA (24mer of polyadenylic acid) at 80°C over a pH range from 4.2 to 9.3. RNA was most stable in the neutral pH range, with a half-life ~5 h, but at higher and lower pH ranges the half-life decreased to ~1 h. These results suggest that if RNA was somehow incorporated into a primitive form of RNA-based thermophilic life, either it must be protected from random hydrolytic events, or the rate of synthesis must exceed the rate of hydrolysis.

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Reagents and Synthetic Methods 30. Practical and Improved Method for Formylating Amino Compounds by Means of Formic Acid-Dimethylformamide System

Cited by 10 publications

References 17 publications

Origin of Informational Polymers: The Concurrent Roles of Formamide and Phosphates

Origin of Informational Polymers: The Concurrent Roles of Formamide and Phosphates

Prebiotic Synthesis of N-Formylaminonitriles and Derivatives in Formamide

Catalytic effects of Murchison Material: Prebiotic Synthesis and Degradation of RNA Precursors

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