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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Main Authors: Evgenii P. Talsi, Anna A. Bryliakova, Roman V. Ottenbacher, Tatyana V. Rybalova, Konstantin P. Bryliakov
Format: Article
Language:English
Published: American Association for the Advancement of Science 2019-01-01
Series:Research
Online Access:http://dx.doi.org/10.34133/2019/4756025
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spelling 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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