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Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes

Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a ge...

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Autores principales: Song, Shihua, Zhou, Jing, Fu, Chunling, Ma, Shengming
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6355870/
https://www.ncbi.nlm.nih.gov/pubmed/30705274
http://dx.doi.org/10.1038/s41467-018-07908-1
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author Song, Shihua
Zhou, Jing
Fu, Chunling
Ma, Shengming
author_facet Song, Shihua
Zhou, Jing
Fu, Chunling
Ma, Shengming
author_sort Song, Shihua
collection PubMed
description Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a general palladium-catalyzed asymmetrization of readily available racemic 2,3-allenylic carbonates with different types of non-substituted and 2-substituted malonates using (R)-(−)-DTBM-SEGPHOS as the preferred ligand to afford 1,3-disubstituted chiral allenes with 90~96% ee. This protocol has been applied to the first enantioselective synthesis of natural product, (R)-traumatic lactone. Control experiments showed that in addition to the chiral ligand, conducting this transformation via Procedure C, which excludes the extensive prior coordination of the allene unit in the starting allene with Pd forming a species without the influence of the chiral ligand, is crucial for the observed high enantioselectivity.
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spelling pubmed-63558702019-02-04 Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes Song, Shihua Zhou, Jing Fu, Chunling Ma, Shengming Nat Commun Article Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a general palladium-catalyzed asymmetrization of readily available racemic 2,3-allenylic carbonates with different types of non-substituted and 2-substituted malonates using (R)-(−)-DTBM-SEGPHOS as the preferred ligand to afford 1,3-disubstituted chiral allenes with 90~96% ee. This protocol has been applied to the first enantioselective synthesis of natural product, (R)-traumatic lactone. Control experiments showed that in addition to the chiral ligand, conducting this transformation via Procedure C, which excludes the extensive prior coordination of the allene unit in the starting allene with Pd forming a species without the influence of the chiral ligand, is crucial for the observed high enantioselectivity. Nature Publishing Group UK 2019-01-31 /pmc/articles/PMC6355870/ /pubmed/30705274 http://dx.doi.org/10.1038/s41467-018-07908-1 Text en © The Author(s) 2019 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Song, Shihua
Zhou, Jing
Fu, Chunling
Ma, Shengming
Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
title Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
title_full Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
title_fullStr Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
title_full_unstemmed Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
title_short Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
title_sort catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6355870/
https://www.ncbi.nlm.nih.gov/pubmed/30705274
http://dx.doi.org/10.1038/s41467-018-07908-1
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