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...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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American Association for the Advancement of Science (AAAS)
2019-01-01
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| Series: | Research |
| Online Access: | http://dx.doi.org/10.34133/2019/4756025 |
| _version_ | 1797286135766974464 |
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| author | Evgenii P. Talsi Anna A. Bryliakova Roman V. Ottenbacher Tatyana V. Rybalova Konstantin P. Bryliakov |
| author_facet | Evgenii P. Talsi Anna A. Bryliakova Roman V. Ottenbacher Tatyana V. Rybalova Konstantin P. Bryliakov |
| author_sort | Evgenii P. Talsi |
| collection | DOAJ |
| 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. |
| first_indexed | 2024-03-07T18:13:48Z |
| format | Article |
| id | doaj.art-650c1155ecec4211aa8cffc5635ff8b1 |
| institution | Directory Open Access Journal |
| issn | 2639-5274 |
| language | English |
| last_indexed | 2024-03-07T18:13:48Z |
| publishDate | 2019-01-01 |
| publisher | American Association for the Advancement of Science (AAAS) |
| record_format | Article |
| series | Research |
| spelling | doaj.art-650c1155ecec4211aa8cffc5635ff8b12024-03-02T07:38:01ZengAmerican Association for the Advancement of Science (AAAS)Research2639-52742019-01-01201910.34133/2019/4756025Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality AmplificationEvgenii P. Talsi0Anna A. Bryliakova1Roman V. Ottenbacher2Tatyana V. Rybalova3Konstantin P. Bryliakov4Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia; Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, RussiaBoreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, RussiaNovosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia; Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, RussiaNovosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia; Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentieva 9, Novosibirsk 630090, RussiaNovosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia; Boreskov 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 |
| spellingShingle | Evgenii P. Talsi Anna A. Bryliakova Roman V. Ottenbacher Tatyana V. Rybalova Konstantin P. Bryliakov Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification Research |
| title | 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_short | 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 |
| url | http://dx.doi.org/10.34133/2019/4756025 |
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