Possible chemical and physical scenarios towards biological homochirality

Sallembien, Quentin; Bouteiller, Laurent; Crassous, Jeanne; Raynal, Matthieu

doi:10.1039/d1cs01179k

Cited by 90 publications

(54 citation statements)

References 586 publications

(1,021 reference statements)

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“…149 Obviously, the chiral stereoselectivity process in this way of life is the key point. 150,151 Fruitful asymmetric Strecker reactions and, thus, optically active a-amino nitriles and proteinogenic and nonproteinogenic a-amino acids can be achieved through two general strategies: (1) the nucleophilic addition of cyanide to chiral nonracemic imines and (2) the catalytic Scheme 15 Preparation of acid heterogeneous "metal-organic fragment mixed" catalysts and their use in the S-3-CR condensation.…”

Section: Asymmetric S-3-cr Condensations Under Nanocatalysis?mentioning

confidence: 99%

Nanostructured silicate catalysts for environmentally benign Strecker-type reactions:status quoandquo vadis

Kouznetsov

Hernández

2022

RSC Adv.

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Section: Asymmetric S-3-cr Condensations Under Nanocatalysis?mentioning

confidence: 99%

Nanostructured silicate catalysts for environmentally benign Strecker-type reactions:status quoandquo vadis

Kouznetsov

Hernández

2022

RSC Adv.

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“…Interestingly, despite the detection of over 20 prochiral molecules in the ISM, we were surprised to note that the significance of prochirality in interstellar chemistry has been severely understated in the literature. In fact, to the extent we exhaustively searched, the phrases “prochiral”/”prochirality”/”prochiral molecule” themselves barely appear not more than ∼a dozen times in the literature of astrochemistry and interstellar chemistry. − Even therein, the aforementioned phrases appeared casually in scattered contexts, and the chemistry associated with prochirality was not discussed at all. One reason could perhaps be that, until recently no chiral molecule was detected in the ISM.…”

Section: Introductionmentioning

confidence: 99%

Possible Role of Metal-Ions in the Chemistry of Prochirality and the Origin of Chirality in the Interstellar Medium

Thripati

Gautam

Ramabhadran

2023

ACS Earth Space Chem.

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Propylene oxide (c-C 3 H 6 O) is the first chiral molecule detected in the interstellar medium (ISM). Its recent detection has opened up newer avenues to be explored in interstellar chemistry. On earth, metal-ions play a preeminent role in the chemistry of chirality and prochirality. Taking a cue from this idea, we computationally investigate the possible role of metal-ions in (a) the origin of chirality in the ISM and (b) advancing interstellar prochiral chemistry; noting that prochirality is a severely understudied concept in astrochemistry. The gas-phase reactions of ethylene, and propylene with OOH radical to lead to the formation of ethylene oxide and propylene oxide respectively were noted to be excellent model reactions, and have been chosen to examine the role of the metal-ions. The interstellar metal-ions being studied (viz. Al + , Mg + , and Mg 2+ ) are considered in three different forms�as bare metal-ions, or as hydrated metal-ions bound to one molecule of water, and as part of a neutral molecule. Carefully calibrated electronic structure calculations (CCSD(T) and DFT) were used to obtain the relevant saddle points (minimum energy structures and transition states). One key conclusion from this work is that, metal-ions, regardless of what form they are in, lead to the barrierless formation of the epoxides, thereby facilitating the generation of interstellar chirality. The key chemical, and astrochemical facets involved in the chemistry of metal-ions in the circumstellar envelope of IRC+10216 are also discussed herein in detail. This work further recommends the detection of four molecules in the ISM, namely, aziridine, methyl aziridine, 2-amino-3-hydroxy propane, and 2-hydroxy-3-amino propane. Lastly, a foremost point to emerge out of this study and related contemporary works probing the chemistry of metal-ions in the ISM is that metal-ions may act as the glue connecting interstellar gas-phase chemistry with the surface chemistry occurring on ice-grains, and could aid in the unravelling of complex and new aspects in astrochemistry.

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“…The amplification of molecular asymmetry in helical macromolecules is the transcription of a small chiral bias into a large preference for a particular helical screw sense. It is a phenomenon of great interest not only for the understanding of the origin of homochirality in biological systems but also for the production of chiroptically active materials from components of minimal enantiomeric purity. − One of the amplification phenomena first discovered in synthetic polymers was observed in polyisocyanates by Green and co-workers. Polyisocyanates are a class of dynamic covalent polymers with interconvertible left-handed ( M -) and right-handed ( P -) helical configurations.…”

Section: Introductionmentioning

confidence: 99%

Amplification of Molecular Asymmetry during the Hierarchical Self-Assembly of Foldable Azobenzene Dyads into Nanotoroids and Nanotubes

2022

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The amplification of molecular asymmetry through self-assembly is a phenomenon that not only comprehends the origin of homochirality in nature but also produces chiroptically active functional materials from molecules with minimal enantiomeric purity. Understanding how molecular asymmetry can be transferred and amplified into higher-order structures in a hierarchical selfassembly system is important but still unexplored. Herein, we present an intriguing example of the amplification of molecular asymmetry in hierarchically self-assembled nanotubes that feature discrete and isolatable toroidal intermediates. The hierarchical self-assembly is initiated via asymmetric intramolecular folding of scissor-shaped azobenzene dyads furnished with chiral side chains. When scalemic mixtures of the enantiomers are dissolved in a non-polar solvent and cooled to 20 °C, single-handed nanotoroids are formed, as confirmed using atomic force microscopy and circular dichroism analyses. A strong majority-rules effect at the nanotoroid level is observed and can be explained by a low mismatch penalty and a high helix-reversal penalty. The single-handed nanotoroids stack upon cooling to 0 °C to exclusively afford their respective single-handed nanotubes. Thus, the same degree of amplification of molecular asymmetry is realized at the nanotube level. The internal packing efficiency of molecules within nanotubes prepared from the pure enantiomers or their scalemic mixtures is likely different, as suggested by the absence of higher-order structure (supercoil) formation in the latter. Xray diffraction analysis of the anisotropically oriented nanotube films revealed looser molecular packing within the scalemic nanotubes, which clearly reflects the lower enantiomeric purity of their internal chiral side chains.

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Possible chemical and physical scenarios towards biological homochirality

Abstract: The most plausible chemical and physical scenarios towards biological homochirality are critically reviewed, with an emphasis on the phenomena leading to the creation and enhancement of an optical bias for the building blocks of life.

Cited by 90 publications

References 586 publications

Nanostructured silicate catalysts for environmentally benign Strecker-type reactions:status quoandquo vadis

Nanostructured silicate catalysts for environmentally benign Strecker-type reactions:status quoandquo vadis

Possible Role of Metal-Ions in the Chemistry of Prochirality and the Origin of Chirality in the Interstellar Medium

Amplification of Molecular Asymmetry during the Hierarchical Self-Assembly of Foldable Azobenzene Dyads into Nanotoroids and Nanotubes

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