Isotope chirality in long‐armed multifunctional organosilicon (“<scp>Cephalopod</scp>”) molecules

Barabás, Béla; Kurdi, Róbert; Zucchi, Claudia; Pályi, Gyula

doi:10.1002/chir.22865

Cited by 7 publications

(1 citation statement)

References 89 publications

(66 reference statements)

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“…The neglected carbon, nitrogen, and oxygen isotope chirality of many organic compounds on Earth can therefore be discriminated by asymmetric autocatalysis with amplification of the extremely small chiral influence between 13 C/ 12 C, 15 N/ 14 N and 18 O/ 16 O. 108,109)…”

Section: Examination Of the Origins Of Chirality By Using Asymmetric mentioning

confidence: 99%

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Soai

2019

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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Biological homochirality, such as that of l -amino acids, has been a puzzle with regards to the chemical origin of life. Asymmetric autocatalysis is a reaction in which a chiral product acts as an asymmetric catalyst to produce more of itself in the same absolute configuration. 5-Pyrimidyl alkanol was found to act as an asymmetric autocatalyst in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde. Asymmetric autocatalysis of 2-alkynyl-5-pyrimidyl alkanol with an extremely low enantiomeric excess of ca. 0.00005% exhibited significant asymmetric amplification to afford the same pyrimidyl alkanol with >99.5% enantiomeric excess and with an increase in the quantity of the same compound. We have employed asymmetric autocatalysis to examine the origin of homochirality. Asymmetric autocatalysis triggered by circularly polarized light, chiral minerals such as quartz, chiral organic crystals composed of achiral compounds gave highly enantioenriched pyrimidyl alkanol with absolute configurations corresponding with those of the chiral triggers. Absolute asymmetric synthesis without the intervention of any chiral factor was achieved. Chiral isotopomers acted as chiral triggers of asymmetric autocatalysis.

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Section: Examination Of the Origins Of Chirality By Using Asymmetric mentioning

confidence: 99%

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Soai

2019

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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Symmetry Breaking and Autocatalytic Amplification in Soai Reaction Confined within UiO‐MOFs under Heterogenous Conditions.

Rotunno

Kaur

Lazzarini

et al. 2021

Chemistry An Asian Journal

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Symmetry breaking is observed in the Soai reaction in a confinement environment provided by zirconium‐based UiO‐MOFs used as crystalline sponges. Subsequent reaction of encapsulated Soai aldehyde with Zn(i‐Pr)2 vapour promoted absolute asymmetric synthesis of the corresponding alkanol. ATR‐IR and NMR confirm integration of aldehyde into the porous material, and a similar localization of newly formed chiral alkanol after reaction. Despite the confinement, the Soai reaction exhibits significant activity and autocatalytic amplification. Comparative catalytic studies with various UiO‐MOFs indicate different outcomes in terms of enantiomeric excess, handedness distribution of the product and reaction rate, when compared to pristine solid Soai aldehyde, while the crystalline MOF remains highly stable to action of Zn(iPr)2 vapour. This is an unprecedented example of absolute asymmetric synthesis using MOFs.

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Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate

2020

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In contrast to the homogenous phase, absolute asymmetric amplification of pyridine alkanol is observed under heterogenous conditions. The reaction of iPr2Zn vapor on a solid powder of pyridine carbaldehyde induced autocatalytic amplification of chirality providing the alkanol product with an enantiopurity up to 90 % ee. In this study, side products were identified and their formation is traced back to redox pathways involving hydride transfer, namely a chiral ester resulting most probably from a disproportionation of the starting aldehyde into a hemiacetal and subsequent hydride loss following a Claisen‐Tishchenko mechanism. These observations provide new perspectives in the elucidation of the mechanism of amplification of chirality in the Soai reaction.

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Isotope chirality in long‐armed multifunctional organosilicon (“Cephalopod”) molecules

Cited by 7 publications

References 89 publications

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Symmetry Breaking and Autocatalytic Amplification in Soai Reaction Confined within UiO‐MOFs under Heterogenous Conditions.

Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate

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