Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2
The kinetic resolution of racemic epoxides using the carbon dioxide (CO2) molecule is of significant practical interest because the reaction yields the valuable products – enantiomerically enriched cyclic carbonates (1,3-dioxolan-2-ones), along with the remaining opposite enantiomer of the epoxide....
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| Format: | Article |
| Language: | English |
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Elsevier
2024-12-01
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| Series: | Tetrahedron Chem |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666951X24000548 |
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| author | Mikhail A. Emelyanov Alexander V. Bachinskiy Yana V. Derkach Vasiliy A. Chaliy Alexander F. Smol'yakov Michael G. Medvedev Aleksei A. Titov Victor I. Maleev Vladimir A. Larionov |
| author_facet | Mikhail A. Emelyanov Alexander V. Bachinskiy Yana V. Derkach Vasiliy A. Chaliy Alexander F. Smol'yakov Michael G. Medvedev Aleksei A. Titov Victor I. Maleev Vladimir A. Larionov |
| author_sort | Mikhail A. Emelyanov |
| collection | DOAJ |
| description | The kinetic resolution of racemic epoxides using the carbon dioxide (CO2) molecule is of significant practical interest because the reaction yields the valuable products – enantiomerically enriched cyclic carbonates (1,3-dioxolan-2-ones), along with the remaining opposite enantiomer of the epoxide. However, one is the main challenges in this direction is the absence of the universal and efficient chiral catalytic systems for the resolution of different epoxides by CO2 with a high selectivity factor (s). In this context, we herein present a perspective proof-of-concept approach for the improvement of stereoselectivity in the resolution of terminal epoxides by a rational design of an appropriate chiral molecular pocket in a Ni(II) complex based on commercially available (S)-(2-aminomethyl)pyrrolidine and 3,5-di-tert-butylsalicylaldehyde. The obtained chiral Ni(II) complex with iodide-anion catalyzes the kinetic resolution of epoxides by CO2 with s-factor up to 7.8, while the addition of a suitable chiral ligand to this system, particularly, (S)-(2-anilinomethyl)pyrrolidine led to the increasing of s-factor up to 11.5 in the case of challenging styrene oxide (ee of styrene cyclic carbonate was 82%) which is being one of the best results for this substrate to date. It is gratifying to note that even achiral co-ligands can be used, greatly simplifying the catalytic system. The experimental and spectral data and DFT calculations revealed the mechanism of catalysis and enantioselection. |
| format | Article |
| id | doaj-art-c4fca50929eb4b7db189ffe5dc78a1f4 |
| institution | DOAJ |
| issn | 2666-951X |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Tetrahedron Chem |
| spelling | doaj-art-c4fca50929eb4b7db189ffe5dc78a1f42025-08-20T02:49:05ZengElsevierTetrahedron Chem2666-951X2024-12-011210011510.1016/j.tchem.2024.100115Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2Mikhail A. Emelyanov0Alexander V. Bachinskiy1Yana V. Derkach2Vasiliy A. Chaliy3Alexander F. Smol'yakov4Michael G. Medvedev5Aleksei A. Titov6Victor I. Maleev7Vladimir A. Larionov8A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian FederationA.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian FederationN.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky prospect 47, 119991, Moscow, Russian FederationN.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky prospect 47, 119991, Moscow, Russian FederationA.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian FederationN.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky prospect 47, 119991, Moscow, Russian Federation; HSE University, Myasnitskaya ulitsa 20, 101000, Moscow, Russian FederationA.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian FederationA.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian FederationA.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian Federation; Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklaya Str. 6, 117198, Moscow, Russian Federation; Corresponding author. A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, bld. 1, 119334, Moscow, Russian Federation.The kinetic resolution of racemic epoxides using the carbon dioxide (CO2) molecule is of significant practical interest because the reaction yields the valuable products – enantiomerically enriched cyclic carbonates (1,3-dioxolan-2-ones), along with the remaining opposite enantiomer of the epoxide. However, one is the main challenges in this direction is the absence of the universal and efficient chiral catalytic systems for the resolution of different epoxides by CO2 with a high selectivity factor (s). In this context, we herein present a perspective proof-of-concept approach for the improvement of stereoselectivity in the resolution of terminal epoxides by a rational design of an appropriate chiral molecular pocket in a Ni(II) complex based on commercially available (S)-(2-aminomethyl)pyrrolidine and 3,5-di-tert-butylsalicylaldehyde. The obtained chiral Ni(II) complex with iodide-anion catalyzes the kinetic resolution of epoxides by CO2 with s-factor up to 7.8, while the addition of a suitable chiral ligand to this system, particularly, (S)-(2-anilinomethyl)pyrrolidine led to the increasing of s-factor up to 11.5 in the case of challenging styrene oxide (ee of styrene cyclic carbonate was 82%) which is being one of the best results for this substrate to date. It is gratifying to note that even achiral co-ligands can be used, greatly simplifying the catalytic system. The experimental and spectral data and DFT calculations revealed the mechanism of catalysis and enantioselection.http://www.sciencedirect.com/science/article/pii/S2666951X24000548Kinetic resolutionCarbon dioxide fixationChiral nickel(II) complexEpoxideCyclic carbonate |
| spellingShingle | Mikhail A. Emelyanov Alexander V. Bachinskiy Yana V. Derkach Vasiliy A. Chaliy Alexander F. Smol'yakov Michael G. Medvedev Aleksei A. Titov Victor I. Maleev Vladimir A. Larionov Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 Tetrahedron Chem Kinetic resolution Carbon dioxide fixation Chiral nickel(II) complex Epoxide Cyclic carbonate |
| title | Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 |
| title_full | Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 |
| title_fullStr | Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 |
| title_full_unstemmed | Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 |
| title_short | Design of a chiral molecular pocket in a Ni(II) complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with CO2 |
| title_sort | design of a chiral molecular pocket in a ni ii complex to improve stereoselectivity in the kinetic resolution of racemic epoxides with co2 |
| topic | Kinetic resolution Carbon dioxide fixation Chiral nickel(II) complex Epoxide Cyclic carbonate |
| url | http://www.sciencedirect.com/science/article/pii/S2666951X24000548 |
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