Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification
Oxidative kinetic resolution of 1-phenylethanol in the presence of manganese complexes, bearing conformationally nonrigid achiral bis-amine-bis-pyridine ligands, in the absence of any exogenous chiral additives, is reported. The only driving force for the chiral discrimination is the small initial e...
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doaj-650c1155ecec4211aa8cffc5635ff8b12020-11-25T00:56:43ZengAmerican Association for the Advancement of ScienceResearch2639-52742019-01-01201910.34133/2019/4756025Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality AmplificationEvgenii P. Talsi0Evgenii P. Talsi1Anna A. Bryliakova2Roman V. Ottenbacher3Roman V. Ottenbacher4Tatyana V. Rybalova5Tatyana V. Rybalova6Konstantin P. Bryliakov7Konstantin P. Bryliakov8Novosibirsk State University,Pirogova 2,Novosibirsk 630090,RussiaBoreskov Institute of Catalysis,Pr. Lavrentieva 5,Novosibirsk 630090,RussiaBoreskov Institute of Catalysis,Pr. Lavrentieva 5,Novosibirsk 630090,RussiaNovosibirsk State University,Pirogova 2,Novosibirsk 630090,RussiaBoreskov Institute of Catalysis,Pr. Lavrentieva 5,Novosibirsk 630090,RussiaNovosibirsk State University,Pirogova 2,Novosibirsk 630090,RussiaVorozhtsov Novosibirsk Institute of Organic Chemistry,Pr. Lavrentieva 9,Novosibirsk 630090,RussiaNovosibirsk State University,Pirogova 2,Novosibirsk 630090,RussiaBoreskov Institute of Catalysis,Pr. Lavrentieva 5,Novosibirsk 630090,RussiaOxidative kinetic resolution of 1-phenylethanol in the presence of manganese complexes, bearing conformationally nonrigid achiral bis-amine-bis-pyridine ligands, in the absence of any exogenous chiral additives, is reported. The only driving force for the chiral discrimination is the small initial enantiomeric imbalance of the scalemic (nonracemic) substrate: the latter dynamically controls the chirality of the catalyst, serving itself as the chiral auxiliary. In effect, the ee of 1-phenylethanol increases monotonously over the reaction course. This dynamic control of catalyst chirality by the substrate has been unprecedented; a consistent kinetic model for this process is presented. The reported catalyzed substrate self-enantioenrichment mechanism is discussed in relation to the problem of prebiotic chirality amplification.http://dx.doi.org/10.34133/2019/4756025 |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Evgenii P. Talsi Evgenii P. Talsi Anna A. Bryliakova Roman V. Ottenbacher Roman V. Ottenbacher Tatyana V. Rybalova Tatyana V. Rybalova Konstantin P. Bryliakov Konstantin P. Bryliakov |
spellingShingle |
Evgenii P. Talsi Evgenii P. Talsi Anna A. Bryliakova Roman V. Ottenbacher Roman V. Ottenbacher Tatyana V. Rybalova Tatyana V. Rybalova Konstantin P. Bryliakov Konstantin P. Bryliakov Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification Research |
author_facet |
Evgenii P. Talsi Evgenii P. Talsi Anna A. Bryliakova Roman V. Ottenbacher Roman V. Ottenbacher Tatyana V. Rybalova Tatyana V. Rybalova Konstantin P. Bryliakov Konstantin P. Bryliakov |
author_sort |
Evgenii P. Talsi |
title |
Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification |
title_short |
Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification |
title_full |
Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification |
title_fullStr |
Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification |
title_full_unstemmed |
Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification |
title_sort |
chiral autoamplification meets dynamic chirality control to suggest nonautocatalytic chemical model of prebiotic chirality amplification |
publisher |
American Association for the Advancement of Science |
series |
Research |
issn |
2639-5274 |
publishDate |
2019-01-01 |
description |
Oxidative kinetic resolution of 1-phenylethanol in the presence of manganese complexes, bearing conformationally nonrigid achiral bis-amine-bis-pyridine ligands, in the absence of any exogenous chiral additives, is reported. The only driving force for the chiral discrimination is the small initial enantiomeric imbalance of the scalemic (nonracemic) substrate: the latter dynamically controls the chirality of the catalyst, serving itself as the chiral auxiliary. In effect, the ee of 1-phenylethanol increases monotonously over the reaction course. This dynamic control of catalyst chirality by the substrate has been unprecedented; a consistent kinetic model for this process is presented. The reported catalyzed substrate self-enantioenrichment mechanism is discussed in relation to the problem of prebiotic chirality amplification. |
url |
http://dx.doi.org/10.34133/2019/4756025 |
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1715892744320188416 |