Cyclotriphosphate: A Brief History, Recent Developments, and Perspectives in Synthesis

Bezold, Dominik; Dürr, Tobias; Singh, Jyoti; Jessen, Henning J.

doi:10.1002/chem.201904433

Cited by 21 publications

(26 citation statements)

References 88 publications

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“…In order to explore this reactivity, sodium trimetaphosphate is a possible alternative; it can be generated by both volcanic eruptions 25 and condensation of phosphates 44,45 . Furthermore, sodium trimetaphosphate has already been shown to produce phosphorylation in the presence of various reagents [46][47][48] . It contains three phosphoric anhydride bonds (P-O-P) that may be considered as "high-energy bonds" in aqueous solution, meaning that their hydrolysis is exergonic.…”

Section: Carbamoyl Phosphate Ammonolysismentioning

confidence: 99%

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

Ter-Ovanessian

Rigaud

Mezzetti

et al. 2021

Sci Rep

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The first step of pyrimidine synthesis along the orotate pathway is studied to test the hypothesis of geochemical continuity of protometabolic pathways at the origins of life. Carbamoyl phosphate (CP) is the first high-energy building block that intervenes in the in vivo synthesis of the uracil ring of UMP. Thus, the likelihood of its occurrence in prebiotic conditions is investigated herein. The evolution of carbamoyl phosphate in water and in ammonia aqueous solutions without enzymes was characterised using ATR-IR, 31P and 13C spectroscopies. Carbamoyl phosphate initially appears stable in water at ambient conditions before transforming to cyanate and carbamate/hydrogenocarbonate species within a matter of hours. Cyanate, less labile than CP, remains a potential carbamoylating agent. In the presence of ammonia, CP decomposition occurs more rapidly and generates urea. We conclude that CP is not a likely prebiotic reagent by itself. Alternatively, cyanate and urea may be more promising substitutes for CP, because they are both “energy-rich” (high free enthalpy molecules in aqueous solutions) and kinetically inert regarding hydrolysis. Energy-rich inorganic molecules such as trimetaphosphate or phosphoramidates were also explored for their suitability as sources of carbamoyl phosphate. Although these species did not generate CP or other carbamoylating agents, they exhibited energy transduction, specifically the formation of high-energy P–N bonds. Future efforts should aim to evaluate the role of carbamoylating agents in aspartate carbamoylation, which is the following reaction in the orotate pathway.

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Section: Carbamoyl Phosphate Ammonolysismentioning

confidence: 99%

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

Ter-Ovanessian

Rigaud

Mezzetti

et al. 2021

Sci Rep

View full text Add to dashboard Cite

show abstract

“…In order to explore this reactivity, sodium trimetaphosphate is a possible alternative; it can be generated by both volcanic eruptions [25] and condensation of phosphates [44] [45]. Furthermore, sodium trimetaphosphate has already been shown to produce phosphorylation in the presence of various reagents [46] [47] [48]. It contains three phosphoric anhydride bonds (P-O-P) that may be considered as "high-energy bonds" in aqueous solution, meaning that their hydrolysis is exergonic.…”

Section: Trimetaphosphate (P3m) Hydrolysismentioning

confidence: 99%

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

Ter-Ovanessian

Rigaud

Mezzetti

et al. 2021

Preprint

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The first step of pyrimidine synthesis along the orotate pathway is studied to test the hypothesis of geochemical continuity of protometabolic pathways at the origins of life. Carbamoyl phosphate (CP) is the first high-energy building block that intervenes in the in vivo synthesis of the uracil ring of UMP. Thus, the likelihood of its occurrence in prebiotic conditions is investigated herein. The evolution of carbamoyl phosphate in water and in ammonia aqueous solutions without enzymes was characterised using ATR-IR, 31P and 13C spectroscopies. Carbamoyl phosphate initially appears stable in water at ambient conditions before transforming to cyanate and carbamate/hydrogenocarbonate species within a matter of hours. Cyanate, less labile than CP, remains a potential carbamoylating agent. In the presence of ammonia, CP decomposition occurs more rapidly and generates urea. We conclude that CP is not a likely prebiotic reagent by itself. Alternatively, cyanate and urea may be more promising substitutes for CP, because they are both “energy-rich” (high free enthalpy molecules in aqueous solutions) and kinetically inert regarding hydrolysis. Energy-rich inorganic molecules such as trimetaphosphate or phosphoramidates were also explored for their suitability as sources of carbamoyl phosphate. Although these species did not generate CP or other carbamoylating agents, they exhibited energy transduction, specifically the formation of high-energy P-N bonds. Future efforts should aim to evaluate the role of carbamoylating agents in aspartate carbamoylation, which is the following reaction in the orotate pathway

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“…Then, we present the synthetic strategies to obtain dinucleotides. Pyrophosphate bond formation has been addressed in some recent reviews and book chapters [1,[13][14][15]. The current review focuses on methods reported for the synthesis of dinucleoside 5′,5′-polyphosphates, especially those of biological and pharmacological interest.…”

Section: Interaction Of Dnps With Purine and Pyrimidine Receptorsmentioning

confidence: 99%

Synthetic Strategies for Dinucleotides Synthesis

et al. 2019

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Dinucleoside 5′,5′-polyphosphates (DNPs) are endogenous substances that play important intra- and extracellular roles in various biological processes, such as cell proliferation, regulation of enzymes, neurotransmission, platelet disaggregation and modulation of vascular tone. Various methodologies have been developed over the past fifty years to access these compounds, involving enzymatic processes or chemical procedures based either on P(III) or P(V) chemistry. Both solution-phase and solid-support strategies have been developed and are reported here. Recently, green chemistry approaches have emerged, offering attracting alternatives. This review outlines the main synthetic pathways for the preparation of dinucleoside 5′,5′-polyphosphates, focusing on pharmacologically relevant compounds, and highlighting recent advances.

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Cyclotriphosphate: A Brief History, Recent Developments, and Perspectives in Synthesis

Cited by 21 publications

References 88 publications

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

Carbamoyl phosphate and its substitutes for the uracil synthesis in origins of life scenarios

Synthetic Strategies for Dinucleotides Synthesis

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