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Stereospecific Isomerization of Allylic Halides via Ion Pairs with Induced Noncovalent Chirality
[Image: see text] A regioselective protocol for the synthesis of substituted allylic chlorides, bromides, and fluorides has been established. Remarkably, the method can be applied to the enantioselective synthesis of challenging chiral allylic chlorides. When the allylic halides are treated with the...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7497663/ https://www.ncbi.nlm.nih.gov/pubmed/32383608 http://dx.doi.org/10.1021/acs.orglett.0c01200 |
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author | Martinez-Erro, Samuel García-Vázquez, Víctor Sanz-Marco, Amparo Martín-Matute, Belén |
author_facet | Martinez-Erro, Samuel García-Vázquez, Víctor Sanz-Marco, Amparo Martín-Matute, Belén |
author_sort | Martinez-Erro, Samuel |
collection | PubMed |
description | [Image: see text] A regioselective protocol for the synthesis of substituted allylic chlorides, bromides, and fluorides has been established. Remarkably, the method can be applied to the enantioselective synthesis of challenging chiral allylic chlorides. When the allylic halides are treated with the base triazabicyclodecene as the catalyst, a [1,3]-proton shift takes place, giving the corresponding vinyl halides in excellent yields with excellent Z:E ratios. Furthermore, the [1,3]-proton shift takes place with an outstanding level of chirality transfer from chiral allylic alcohols (≤98%) to give chiral trifluoromethylated vinyl chlorides. |
format | Online Article Text |
id | pubmed-7497663 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-74976632020-09-18 Stereospecific Isomerization of Allylic Halides via Ion Pairs with Induced Noncovalent Chirality Martinez-Erro, Samuel García-Vázquez, Víctor Sanz-Marco, Amparo Martín-Matute, Belén Org Lett [Image: see text] A regioselective protocol for the synthesis of substituted allylic chlorides, bromides, and fluorides has been established. Remarkably, the method can be applied to the enantioselective synthesis of challenging chiral allylic chlorides. When the allylic halides are treated with the base triazabicyclodecene as the catalyst, a [1,3]-proton shift takes place, giving the corresponding vinyl halides in excellent yields with excellent Z:E ratios. Furthermore, the [1,3]-proton shift takes place with an outstanding level of chirality transfer from chiral allylic alcohols (≤98%) to give chiral trifluoromethylated vinyl chlorides. American Chemical Society 2020-05-08 2020-06-05 /pmc/articles/PMC7497663/ /pubmed/32383608 http://dx.doi.org/10.1021/acs.orglett.0c01200 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Martinez-Erro, Samuel García-Vázquez, Víctor Sanz-Marco, Amparo Martín-Matute, Belén Stereospecific Isomerization of Allylic Halides via Ion Pairs with Induced Noncovalent Chirality |
title | Stereospecific Isomerization of Allylic Halides via
Ion Pairs with Induced Noncovalent Chirality |
title_full | Stereospecific Isomerization of Allylic Halides via
Ion Pairs with Induced Noncovalent Chirality |
title_fullStr | Stereospecific Isomerization of Allylic Halides via
Ion Pairs with Induced Noncovalent Chirality |
title_full_unstemmed | Stereospecific Isomerization of Allylic Halides via
Ion Pairs with Induced Noncovalent Chirality |
title_short | Stereospecific Isomerization of Allylic Halides via
Ion Pairs with Induced Noncovalent Chirality |
title_sort | stereospecific isomerization of allylic halides via
ion pairs with induced noncovalent chirality |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7497663/ https://www.ncbi.nlm.nih.gov/pubmed/32383608 http://dx.doi.org/10.1021/acs.orglett.0c01200 |
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