Mechanochemical Activation of Iron Cyano Complexes: A Prebiotic Impact Scenario for the Synthesis of α‐Amino Acid Derivatives

Bolm, Carsten; Mocci, Rita; Schumacher, Christian; Turberg, Mathias; Puccetti, Francesco; Hernández, José G.

doi:10.1002/ange.201713109

Cited by 45 publications

(19 citation statements)

References 55 publications

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“…10,11 Furthermore, we see no reason why the herein presented reaction sequences should not be compatible with industrial-scale roller mills and/or continuous mechanochemical manufacture via twin screw extrusion, 56 as has recently been done in the context of small organic molecule targets and metal-organic frameworks. 57,58 Finally, we note that the ability to obtain functional oligonucleotide structures without a bulk solvent might suggest the potential role of solid-state transformations in the early stages of chemical evolution, as recently highlighted by Trapp and co-workers 59 , and Hernández and co-workers 60 .…”

Section: Scheme 5 Synthesis Phosphorothioate Dimers Via Phosphoramidsupporting

confidence: 54%

Mechanochemical Synthesis of Short DNA Fragments

Thorpe

O'Reilly

Friščić

et al. 2020

Chemistry A European J

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We report the general and rapid synthesis of short DNA fragments of controllable sequence and length using multi-step, one-pot mechanochemical reactions, without bulk solvent or the need to isolate intermediates. We demonstrate, for the first time, the multi-step ball milling synthesis of DNA dimers and trimers via phosphoramidite and H-phosphonate chemistries. The use of mechanochemistry allowed for coupling of phosphoramidite monomers to the 5'-hydroxyl group of nucleosides, iodine/water oxidation of the resulting phosphite triester linkage, and removal of the 5'-dimethoxy (DMTr) protecting group in situ and in good yields (up to 60% over three steps) to produce DNA dimers in one-pot manner. Sulphurization of phosphite triester linkages was possible using elemental sulfur yielding the corresponding phosphorothioate DNA dimers in good yield (up to 80% over two steps). By using H-phosphonate chemistry under milling conditions, it was possible to couple, protect the H-phosphonate linkage, and remove the 5'-DMTr protecting group in situ, enabling an one-pot process with good yields comparable to existing solvent-based procedures (up to 65% over three steps, or ca. 87% per step). This work opens the door to creation of solvent-free methodologies for the assembly of complex DNA and RNA therapeutics. File list (2) download file view on ChemRxiv ChemRxiv_manuscript.pdf (537.19 KiB) download file view on ChemRxiv SI_ChemRxiv.pdf (1.50 MiB)

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Section: Scheme 5 Synthesis Phosphorothioate Dimers Via Phosphoramidsupporting

confidence: 54%

Mechanochemical Synthesis of Short DNA Fragments

Thorpe

O'Reilly

Friščić

et al. 2020

Chemistry A European J

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“…Other sources for mechanical energy include tectonics, which might have even been present on the Earth as early as about 4 Ga ago 22 and can likewise occur on asteroids 23 . In addition to possibly introducing organic matter, impact events also lead to a mechanical energy input and under these conditions the synthesis of amino acid derivatives as well as the stability of glycolaldehyde have been shown 24,25 . For laboratory purposes ball milling is the standard procedure for performing mechanochemical reactions 26 , which have been applied to mineral catalysis and even gaseous reactants [27][28][29] .…”

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confidence: 99%

Mineral-mediated carbohydrate synthesis by mechanical forces in a primordial geochemical setting

et al. 2020

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The formation of carbohydrates represents an essential step to provide building blocks and a source of chemical energy in several models for the emergence of life. Formaldehyde, glycolaldehyde and a basic catalyst are the initial components forming a variety of sugar molecules in the cascade-type multi-step formose reaction. While numerous side reactions and even deterioration can be observed in aqueous media, selective prebiotic sugar formation is feasible in solid-state, mechanochemical reactions and might have occurred in early geochemistry. However, the precise role of different basic catalysts and the influence of the atmospheric conditions in the solid-state formose reaction remain unknown. Here we show, that in a primordial scenario the mechanochemical formose reaction is capable to form monosaccharides with a broad variety of mineral classes as catalysts with only minute amounts of side products such as lactic acid or methanol, independent of the atmospheric conditions. The results give insight into recent findings of formose sugars on meteorites and offer a water-free and robust pathway for monosaccharides independent of the external conditions both for the early Earth or an extra-terrestrial setting.

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“…[18] The mechanochemically made rac-a-aminonitriles could then be transformed into rac-a-amino amides by prebiotic routes such as the hydration of nitrilesw ith urea hydrogen peroxide (UHP) or the carbonyl-mediated hydration of nitrilesb yu sing paraformaldehyde (PFA). [18] Complementary routes to access nonchiral unsaturated amino acids derivativesw ere reported as early as 2006 by Frejd and co-workers, [19] and in 2010 by the group of Lamaty. [20] In 2012, Lamaty and co-workers also reported an asymmetrics ynthesis of amino esters derivatives inside ab all mill with yields ranging from 91 to 97 %a nd with up to 75 % ee.…”

Section: Synthesis Of Amino Acidsmentioning

confidence: 99%

“…Moreover, a-aminoacids have been used as valuable synthons in organic chemistry.T his was clearly portrayed by the mechanosynthesis of bioactiveh ydantoins such as the anti-epileptic drug phenytoin ( Figure 2, 17), [27] and by the condensation of l-cysteine with paraformaldehyde, which was reported to afford quantitatively (R)-thiazolidine ( 18). [28a] Similarly, in 2017, Lamaty,M Øtro, and co-workersu tilized ball-milling techniques during the synthesis of proline-proline diketopiperazine frameworks 19.…”

Section: Use and Modification Of Amino Acids In Ball Millsmentioning

confidence: 99%

“…The potential of the mechanochemicala pproach was further demonstrated in ap rebiotic formationo frac-a-aminonitriles 3 by using K 3 [Fe(CN) 6 ]a st he cyanation reagent (Scheme 1b). [18] The mechanochemically made rac-a-aminonitriles could then be transformed into rac-a-amino amides by prebiotic routes such as the hydration of nitrilesw ith urea hydrogen peroxide (UHP) or the carbonyl-mediated hydration of nitrilesb yu sing paraformaldehyde (PFA). [18] Complementary routes to access nonchiral unsaturated amino acids derivativesw ere reported as early as 2006 by Frejd and co-workers, [19] and in 2010 by the group of Lamaty.…”

Section: Synthesis Of Amino Acidsmentioning

confidence: 99%

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From Synthesis of Amino Acids and Peptides to Enzymatic Catalysis: A Bottom‐Up Approach in Mechanochemistry

2018

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Recently, chemical reactions induced or facilitated by mechanical energy have gained recognition in diverse areas of chemical synthesis. In particular, mechanosyntheses of amino acids and short peptides, along with their applications in catalysis, have revealed the high degree of stability of peptide bonds in environments of harsh mechanical stress. These observations quickly led to the recent interest in developing mechanochemical enzymatic reactions. Experimentally, manual grinding, ball-milling techniques, and twin-screw extrusion technology have proven valuable to convey mechanical forces into a chemical synthesis. These practices have enabled the establishment of more sustainable alternatives for chemical synthesis by reducing the use of organic solvents and waste production, thereby having a direct impact on the E-factor of the chemical process. In this Minireview, the series of events that allowed the development of mechanochemical enzymatic reactions are described from a bottom-up perspective.

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Mechanochemical Activation of Iron Cyano Complexes: A Prebiotic Impact Scenario for the Synthesis of α‐Amino Acid Derivatives

Cited by 45 publications

References 55 publications

Mechanochemical Synthesis of Short DNA Fragments

Mechanochemical Synthesis of Short DNA Fragments

Mineral-mediated carbohydrate synthesis by mechanical forces in a primordial geochemical setting

From Synthesis of Amino Acids and Peptides to Enzymatic Catalysis: A Bottom‐Up Approach in Mechanochemistry

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