Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles
In the presence of a copper(II) catalyst, enolizable imines bearing various N-substituents and α-diazo-β-ketoesters undergo denitrogenative and dehydrative condensation to afford highly substituted pyrroles in moderate to good yields with exclusive regioselectivity. The reaction likely involves nucl...
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| Format: | Journal Article |
| Language: | English |
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2018
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| Online Access: | https://hdl.handle.net/10356/89964 http://hdl.handle.net/10220/46433 |
| _version_ | 1811681654535618560 |
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| author | Tan, Wei Wen Yoshikai, Naohiko |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Tan, Wei Wen Yoshikai, Naohiko |
| author_sort | Tan, Wei Wen |
| collection | NTU |
| description | In the presence of a copper(II) catalyst, enolizable imines bearing various N-substituents and α-diazo-β-ketoesters undergo denitrogenative and dehydrative condensation to afford highly substituted pyrroles in moderate to good yields with exclusive regioselectivity. The reaction likely involves nucleophilic addition of the imine nitrogen to a copper carbenoid, tautomerization of the resulting azomethine ylide to an α-enaminoketone, and a subsequent enamine–ketone cyclocondensation. With Yb(OTf)3 as a unique cocatalyst, α-diazo-β-diketones also participate in the same condensation reaction. The present reaction is applicable to acyclic, exocyclic, and endocyclic imines with tolerance of a broad range of functional groups and heterocyclic moieties, thus opening a new convenient route for the synthesis of the lamellarin family of natural products. |
| first_indexed | 2024-10-01T03:44:23Z |
| format | Journal Article |
| id | ntu-10356/89964 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:44:23Z |
| publishDate | 2018 |
| record_format | dspace |
| spelling | ntu-10356/899642023-02-28T19:24:01Z Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles Tan, Wei Wen Yoshikai, Naohiko School of Physical and Mathematical Sciences Condensation Copper Catalyzed DRNTU::Science::Chemistry In the presence of a copper(II) catalyst, enolizable imines bearing various N-substituents and α-diazo-β-ketoesters undergo denitrogenative and dehydrative condensation to afford highly substituted pyrroles in moderate to good yields with exclusive regioselectivity. The reaction likely involves nucleophilic addition of the imine nitrogen to a copper carbenoid, tautomerization of the resulting azomethine ylide to an α-enaminoketone, and a subsequent enamine–ketone cyclocondensation. With Yb(OTf)3 as a unique cocatalyst, α-diazo-β-diketones also participate in the same condensation reaction. The present reaction is applicable to acyclic, exocyclic, and endocyclic imines with tolerance of a broad range of functional groups and heterocyclic moieties, thus opening a new convenient route for the synthesis of the lamellarin family of natural products. NRF (Natl Research Foundation, S’pore) Published version 2018-10-25T08:06:55Z 2019-12-06T17:37:35Z 2018-10-25T08:06:55Z 2019-12-06T17:37:35Z 2015 Journal Article Tan, W. W., & Yoshikai, N. (2015). Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds: modular and regiocontrolled synthesis of multisubstituted pyrroles. Chemical Science, 6(11), 6448-6455. doi:10.1039/c5sc02322j 2041-6520 https://hdl.handle.net/10356/89964 http://hdl.handle.net/10220/46433 10.1039/C5SC02322J en Chemical Science © 2015 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. 8 p. application/pdf |
| spellingShingle | Condensation Copper Catalyzed DRNTU::Science::Chemistry Tan, Wei Wen Yoshikai, Naohiko Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles |
| title | Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles |
| title_full | Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles |
| title_fullStr | Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles |
| title_full_unstemmed | Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles |
| title_short | Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds : modular and regiocontrolled synthesis of multisubstituted pyrroles |
| title_sort | copper catalyzed condensation of imines and α diazo β dicarbonyl compounds modular and regiocontrolled synthesis of multisubstituted pyrroles |
| topic | Condensation Copper Catalyzed DRNTU::Science::Chemistry |
| url | https://hdl.handle.net/10356/89964 http://hdl.handle.net/10220/46433 |
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