Interstellar bromine abundance is consistent with cometary ices from Rosetta

Ligterink, N. F. W.; Kama, M.

doi:10.1051/0004-6361/201732325

Cited by 7 publications

(3 citation statements)

References 46 publications

(57 reference statements)

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“…Our next steps were aimed at finding a more prebiotically plausible catalysis. We shifted from long-chain aldehydes to shorter aldehydes like propanal and exchanged 2,6-lutidine for structurally related bases like collidine or 2-methylquinoline, as all these compounds are proposed to have existed on early Earth. , In the case of 2-bromoacetonitrile, it was shown to form by light-induced radical recombination of interstellar bromine and acetonitrile and was therefore used without modification. , Surprisingly, we observed that the photosensitizer Ru(bpy) 3 Cl 2 was redundant under our reaction conditions and could be omitted without a loss in yield.…”

Section: Photoredox Organocatalytic α-Alkylation With Prebiotically F...mentioning

confidence: 87%

“…26,27 In the case of 2-bromoacetonitrile, it was shown to form by light-induced radical recombination of interstellar bromine and acetonitrile and was therefore used without modification. 28,29 Surprisingly, we observed that the photosensitizer Ru(bpy) 3 Cl 2 was redundant under our reaction conditions and could be omitted without a loss in yield. With our modified reaction conditions, we screened this library and were able to observe product formation for all catalysts 1 (Scheme 3).…”

Section: α-Alkylation With Prebiotically Formed Imidazolidine-4-thionesmentioning

confidence: 99%

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(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution

Bechtel,

Ebeling,

Huber

et al. 2023

Acc. Chem. Res.

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Conspectus Life as we know it is built on complex and perfectly interlocking processes that have evolved over millions of years through evolutionary optimization processes. The emergence of life from nonliving matter and the evolution of such highly efficient systems therefore constitute an enormous synthetic and systems chemistry challenge. Advances in supramolecular and systems chemistry are opening new perspectives that provide insights into living and self-sustaining reaction networks as precursors for life. However, the ab initio synthesis of such a system requires the possibility of autonomous optimization of catalytic properties and, consequently, of an evolutionary system at the molecular level. In this Account, we present our discovery of the formation of substituted imidazolidine-4-thiones (photoredox) organocatalysts from simple prebiotic building blocks such as aldehydes and ketones under Strecker reaction conditions with ammonia and cyanides in the presence of hydrogen sulfide. The necessary aldehydes are formed from CO2 and hydrogen under prebiotically plausible meteoritic or volcanic iron-particle catalysis in the atmosphere of the early Earth. Remarkably, the investigated imidazolidine-4-thiones undergo spontaneous resolution by conglomerate crystallization, opening a pathway for symmetry breaking, chiral amplification, and enantioselective organocatalysis. These imidazolidine-4-thiones enable α-alkylations of aldehydes and ketones by photoredox organocatalysis. Therefore, these photoredox organocatalysts are able to modify their aldehyde building blocks, which leads in an evolutionary process to mutated second-generation and third-generation catalysts. In our experimental studies, we found that this mutation can occur not only by new formation of the imidazolidine core structure of the catalyst from modified aldehyde building blocks or by continuous supply from a pool of available building blocks but also by a dynamic exchange of the carbonyl moiety in ring position 2 of the imidazolidine moiety. Remarkably, it can be shown that by incorporating aldehyde building blocks from their environment, the imidazolidine-4-thiones are able to change and adapt to altering environmental conditions without undergoing the entire formation process. The selection of the mutated catalysts is then based on the different catalytic activities in the modification of the aldehyde building blocks and on the catalysis of subsequent processes that can lead to the formation of molecular reaction networks as progenitors for cellular processes. We were able to show that these imidazolidine-4-thiones not only enable α-alkylations but also facilitate other important transformations, such as the selective phosphorylation of nucleosides to nucleotides as a key step leading to the oligomerization to RNA and DNA. It can therefore be expected that evolutionary processes have already taken place on a small molecular level and have thus developed chemical tools that change over time, representing a hidden layer on the path to enzyma...

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Section: Photoredox Organocatalytic α-Alkylation With Prebiotically F...mentioning

confidence: 87%

Section: α-Alkylation With Prebiotically Formed Imidazolidine-4-thionesmentioning

confidence: 99%

(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution

Bechtel,

Ebeling,

Huber

et al. 2023

Acc. Chem. Res.

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“…Here, we focused on the α‐cyanomethylation, as the products would give access to prebiotically relevant, more complex molecules by hydrolysis of the nitrile group and further transformation of the aldehyde functionality. The existence of 2‐bromoacetonitrile is plausible under the conditions on the Early Earth, formed in a photoinduced radical recombination of interstellar abundant bromine and CH 3 CN . In addition, the sun is considered as an important energy supplier in the resource‐poor environment at that time, whereby photoreactions have been highly probable.…”

Section: Methodsmentioning

confidence: 99%

Prebiotically Plausible Organocatalysts Enabling a Selective Photoredox α‐Alkylation of Aldehydes on the Early Earth

Closs

Fuks

Bechtel

et al. 2020

Chemistry A European J

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Organocatalysis is a powerful approach to extend and (enantio‐) selectively modify molecular structures. Adapting this concept to the Early Earth scenario offers a promising solution to explain their evolution into a complex homochiral world. Herein, we present a class of imidazolidine‐4‐thione organocatalysts, easily accessible from simple molecules available on an Early Earth under highly plausible prebiotic reaction conditions. These imidazolidine‐4‐thiones are readily formed from mixtures of aldehydes or ketones in presence of ammonia, cyanides and hydrogen sulfide in high selectivity and distinct preference for individual compounds of the resulting catalyst library. These organocatalysts enable the enantioselective α‐alkylation of aldehydes under prebiotic conditions and show activities that correlate with the selectivity of their formation. Furthermore, the crystallization of single catalysts as conglomerates opens the pathway for symmetry breaking.

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First Steps of Prebiotic Chemistry Catalyzed by Minerals and Metals

Huber

Trapp

2022

Prebiotic Chemistry and Life's Origin

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The proposed pathways for building block formation in prebiotic chemistry are manifold. Recent advances in the development of modern analytical techniques and methods now allow us to make significant progress in the elucidation and exploration of the origin of life. The aim of this chapter is to give an overview of metal and mineral mediated pathways to complex organic building blocks. The two main focuses will be the role of iron in this context and mineral catalysis in monosaccharide synthesis.

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Interstellar bromine abundance is consistent with cometary ices from Rosetta

Cited by 7 publications

References 46 publications

(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution

(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution

Prebiotically Plausible Organocatalysts Enabling a Selective Photoredox α‐Alkylation of Aldehydes on the Early Earth

First Steps of Prebiotic Chemistry Catalyzed by Minerals and Metals

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