Achiral Inorganic Gypsum Acts as an Origin of Chirality through Its Enantiotopic Surface in Conjunction with Asymmetric Autocatalysis

Matsumoto, Arimasa; Kaimori, Yoshiyasu; Uchida, Mizuki; Omori, Haruna; Kawasaki, Tsuneomi; Soai, Kenso

doi:10.1002/anie.201610099

Cited by 37 publications

(19 citation statements)

References 87 publications

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“…The criticism of the asymmetric autocatalytic model focuses on the high sensitivity of the outcome of the Soai reaction (which so far has been the only autocatalytic reaction ensuring significant enhancement of enantiomeric excess) to external additives (even not necessarily chiral [ 43 ]), which again puts “chance” in the forefront, bringing into question the capability of the Soai system to function unidirectionally under nonideal reaction conditions. Another point is that organometallic Soai reaction, yet extremely efficient, requires strictly nonaqueous environment, which is not compatible with the presumably partially aqueous environment of the early Earth by the end of the abiotic period of its history.…”

Section: Asymmetric Autocatalytic Reactionmentioning

confidence: 99%

Chemical Mechanisms of Prebiotic Chirality Amplification

Bryliakov

2020

Research

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This review article surveys the recent experimental findings that suggest alternative chemical models of directed chirality amplification at the early, prebiotic Earth. It is believed that the chirality amplification step followed the initial emergence of small enantiomeric imbalance and preceded (as a necessary condition) the occurrence of homochiral biopolymers, assembled from enantiomerically pure building blocks. This work focuses on the chemical nature of possible mechanisms of primordial chirality enhancement, without going into detail of the preceding and subsequent phases of origination of biological homochirality and life on Earth. These mechanisms are discussed through the prism of integrity of biological natural selection and chemical kinetic selection.

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Section: Asymmetric Autocatalytic Reactionmentioning

confidence: 99%

Chemical Mechanisms of Prebiotic Chirality Amplification

Bryliakov

2020

Research

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“…To amplify these enantioimbalances we use Viedma ripening (i.e. attrition‐induced deracemization)—a powerful method to amplify minute enantioimbalances to virtually absolute enantiomeric purity [19–27] . Viedma ripening requires racemizable conglomerates, i.e.…”

Section: Figurementioning

confidence: 99%

Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality

et al. 2020

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Propagation of homochirality plays a crucial role in the discussion on the origin of life. We investigated the role of structurally related enantiopure additives in chiral symmetry breaking during reactive crystallizations. We demonstrate that symmetry breaking can be driven towards the same absolute configuration as the additive if this additive forms an enantiospecific solid solution with the racemate. We observe two antagonistic processes: enantiospecific growth inhibition directs symmetry breaking to the opposite enantiomer following “the rule of reversal”, and enantiospecific solid solution formation that favors homochiral outcome. During continuous grinding, contributions of solid solution formation override contributions of enantiospecific growth inhibition, directing the process towards the absolute configuration of the additive. Collectively, our findings offer a potential mechanism for the propagation of homochirality.

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“…Pyrimidine-5-carbaldehyde 2c was put on the enantiotopic (010) face. Then, the reaction of aldehyde 2c on gypsum with the vapor of i-Pr 2 Zn gave (R)-pyrimidyl alkanol 1c [86]. In contrast, the reaction by exposing on the opposite (0−10) face gave (S)-alkanol 1c.…”

Section: Chiral Crystals Formed From Achiral Organic Compoundsmentioning

confidence: 99%

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

2019

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Pyrimidyl alkanol and related compounds were found to be asymmetric autocatalysts in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde and related aldehydes. In the asymmetric autocatalysis with amplification of enantiomeric excess (ee), the very low ee (ca. 0.00005%) of 2-alkynyl-5-pyrimidyl alkanol was significantly amplified to >99.5% ee with an increase in the amount. By using asymmetric autocatalysis with amplification of ee, several origins of homochirality have been examined. Circularly polarized light, chiral quartz, and chiral crystals formed from achiral organic compounds such as glycine and carbon (13C/12C), nitrogen (15N/14N), oxygen (18O/16O), and hydrogen (D/H) chiral isotopomers were found to act as the origin of chirality in asymmetric autocatalysis. And the spontaneous absolute asymmetric synthesis was also realized without the intervention of any chiral factor.

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Achiral Inorganic Gypsum Acts as an Origin of Chirality through Its Enantiotopic Surface in Conjunction with Asymmetric Autocatalysis

Cited by 37 publications

References 87 publications

Chemical Mechanisms of Prebiotic Chirality Amplification

Chemical Mechanisms of Prebiotic Chirality Amplification

Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

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