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Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones
Catalytic asymmetric variants for functional group transformations based on carbon–carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp(2))–C(sp(2)) σ bond activation and click desymmetrization to form synthetically...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8549799/ https://www.ncbi.nlm.nih.gov/pubmed/34760158 http://dx.doi.org/10.1039/d1sc04558j |
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author | Zhou, Han-Qi Gu, Xing-Wei Zhou, Xiao-Hua Li, Li Ye, Fei Yin, Guan-Wu Xu, Zheng Xu, Li-Wen |
author_facet | Zhou, Han-Qi Gu, Xing-Wei Zhou, Xiao-Hua Li, Li Ye, Fei Yin, Guan-Wu Xu, Zheng Xu, Li-Wen |
author_sort | Zhou, Han-Qi |
collection | PubMed |
description | Catalytic asymmetric variants for functional group transformations based on carbon–carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp(2))–C(sp(2)) σ bond activation and click desymmetrization to form synthetically versatile and value-added oxaspiro products. The operationally straightforward and enantioselective palladium-catalyzed atom-economic annulation process exploits a TADDOL-derived bulky P-ligand bearing a large cavity to control enantioselective spiro-annulation that converts cyclopropenones and cyclic 1,3-diketones into chiral oxaspiro cyclopentenone–lactone scaffolds with good diastereo- and enantio-selectivity. The click-like reaction is a successful methodology with a facile construction of two vicinal carbon quaternary stereocenters and can be used to deliver additional stereocenters during late-state functionalization for the synthesis of highly functionalized or more complex molecules. |
format | Online Article Text |
id | pubmed-8549799 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-85497992021-11-09 Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones Zhou, Han-Qi Gu, Xing-Wei Zhou, Xiao-Hua Li, Li Ye, Fei Yin, Guan-Wu Xu, Zheng Xu, Li-Wen Chem Sci Chemistry Catalytic asymmetric variants for functional group transformations based on carbon–carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp(2))–C(sp(2)) σ bond activation and click desymmetrization to form synthetically versatile and value-added oxaspiro products. The operationally straightforward and enantioselective palladium-catalyzed atom-economic annulation process exploits a TADDOL-derived bulky P-ligand bearing a large cavity to control enantioselective spiro-annulation that converts cyclopropenones and cyclic 1,3-diketones into chiral oxaspiro cyclopentenone–lactone scaffolds with good diastereo- and enantio-selectivity. The click-like reaction is a successful methodology with a facile construction of two vicinal carbon quaternary stereocenters and can be used to deliver additional stereocenters during late-state functionalization for the synthesis of highly functionalized or more complex molecules. The Royal Society of Chemistry 2021-09-20 /pmc/articles/PMC8549799/ /pubmed/34760158 http://dx.doi.org/10.1039/d1sc04558j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Zhou, Han-Qi Gu, Xing-Wei Zhou, Xiao-Hua Li, Li Ye, Fei Yin, Guan-Wu Xu, Zheng Xu, Li-Wen Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
title | Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
title_full | Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
title_fullStr | Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
title_full_unstemmed | Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
title_short | Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
title_sort | enantioselective palladium-catalyzed c(sp(2))–c(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8549799/ https://www.ncbi.nlm.nih.gov/pubmed/34760158 http://dx.doi.org/10.1039/d1sc04558j |
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