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Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition
Development of a general catalytic and highly efficient method utilizing readily available precursors for the regio- and stereoselective construction of bioactive natural-product-inspired spiro architectures remains a formidable challenge in chemical research. Transition metal-catalyzed asymmetric 1...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Elsevier
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6317281/ https://www.ncbi.nlm.nih.gov/pubmed/30612034 http://dx.doi.org/10.1016/j.isci.2018.12.010 |
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author | Shen, Chong Yang, Yuhong Wei, Liang Dong, Wu-Wei Chung, Lung Wa Wang, Chun-Jiang |
author_facet | Shen, Chong Yang, Yuhong Wei, Liang Dong, Wu-Wei Chung, Lung Wa Wang, Chun-Jiang |
author_sort | Shen, Chong |
collection | PubMed |
description | Development of a general catalytic and highly efficient method utilizing readily available precursors for the regio- and stereoselective construction of bioactive natural-product-inspired spiro architectures remains a formidable challenge in chemical research. Transition metal-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides produces numerous N-heterocycles, but reaction control with the regioselectivity opposite to the conventional fashion has rarely been demonstrated. Herein, we report a unique ligand-controlled Cu(I)-catalyzed umpolung-type 1,3-dipolar cycloaddition of azomethine ylide to realize efficient kinetic resolution of racemic alkylidene norcamphors with the concomitant construction of previously inaccessible spiro N-heterocycles with high levels of regio- and stereoselectivity. The success of this methodology relies on the strategy of kinetic resolution, and the serendipitous discovery of a unique ligand-enabled regiospecific cycloaddition, which not only provides evidence for the existence of the minor zwitterionic resonance form in metallated azomethine ylide but also diversifies the existing chemistry of azomethine ylide-involved 1,3-dipolar cycloadditions with rare polarity inversion. |
format | Online Article Text |
id | pubmed-6317281 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Elsevier |
record_format | MEDLINE/PubMed |
spelling | pubmed-63172812019-01-08 Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition Shen, Chong Yang, Yuhong Wei, Liang Dong, Wu-Wei Chung, Lung Wa Wang, Chun-Jiang iScience Article Development of a general catalytic and highly efficient method utilizing readily available precursors for the regio- and stereoselective construction of bioactive natural-product-inspired spiro architectures remains a formidable challenge in chemical research. Transition metal-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides produces numerous N-heterocycles, but reaction control with the regioselectivity opposite to the conventional fashion has rarely been demonstrated. Herein, we report a unique ligand-controlled Cu(I)-catalyzed umpolung-type 1,3-dipolar cycloaddition of azomethine ylide to realize efficient kinetic resolution of racemic alkylidene norcamphors with the concomitant construction of previously inaccessible spiro N-heterocycles with high levels of regio- and stereoselectivity. The success of this methodology relies on the strategy of kinetic resolution, and the serendipitous discovery of a unique ligand-enabled regiospecific cycloaddition, which not only provides evidence for the existence of the minor zwitterionic resonance form in metallated azomethine ylide but also diversifies the existing chemistry of azomethine ylide-involved 1,3-dipolar cycloadditions with rare polarity inversion. Elsevier 2018-12-15 /pmc/articles/PMC6317281/ /pubmed/30612034 http://dx.doi.org/10.1016/j.isci.2018.12.010 Text en © 2018 The Author(s) http://creativecommons.org/licenses/by-nc-nd/4.0/ This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Article Shen, Chong Yang, Yuhong Wei, Liang Dong, Wu-Wei Chung, Lung Wa Wang, Chun-Jiang Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition |
title | Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition |
title_full | Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition |
title_fullStr | Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition |
title_full_unstemmed | Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition |
title_short | Kinetic Resolution of Alkylidene Norcamphors via a Ligand-Controlled Umpolung-Type 1,3-Dipolar Cycloaddition |
title_sort | kinetic resolution of alkylidene norcamphors via a ligand-controlled umpolung-type 1,3-dipolar cycloaddition |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6317281/ https://www.ncbi.nlm.nih.gov/pubmed/30612034 http://dx.doi.org/10.1016/j.isci.2018.12.010 |
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