Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings
In previous work we reported the formal synthesis of the marine macrolide (−)-callyspongiolide through a synthetic approach in which the generation of the key macrocyclic core relies on a ruthenium-catalyzed ring-closing metathesis reaction. However, besides the predicted macrolactone intermediate,...
| Autores: | , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/193700 |
| Acceso en línea: | https://hdl.handle.net/2445/193700 |
| Access Level: | acceso abierto |
| Palabra clave: | Metàtesi (Química) Compostos bioactius Síntesi orgànica Alcaloides Metathesis (Chemistry) Bioactive compounds Organic synthesis Alkaloids |
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Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered ringsDíaz-Ruiz, MarinaUrbina Teixidor, AinaLlor Brunés, NúriaBosch Cartes, JoanAmat Tusón, MercedesMaseras Cuní, FeliuMetàtesi (Química)Compostos bioactiusSíntesi orgànicaAlcaloidesMetathesis (Chemistry)Bioactive compoundsOrganic synthesisAlkaloidsIn previous work we reported the formal synthesis of the marine macrolide (−)-callyspongiolide through a synthetic approach in which the generation of the key macrocyclic core relies on a ruthenium-catalyzed ring-closing metathesis reaction. However, besides the predicted macrolactone intermediate, an undesired cyclooctene was observed. We investigate here the mechanism of this critical step through density functional theory calculations. The results indicate that the chemoselectivity is not under kinetic control but ruled by thermodynamics. This conclusion is further confirmed by additional experimental studies.Elsevier B.V.2023202420222023info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/193700Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1016/j.tet.2022.133016Tetrahedron, 2022https://doi.org/10.1016/j.tet.2022.133016cc-by-nc-nd (c) Elsevier B.V., 2022https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1937002026-05-29T05:05:01Z |
| dc.title.none.fl_str_mv |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| title |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| spellingShingle |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings Díaz-Ruiz, Marina Metàtesi (Química) Compostos bioactius Síntesi orgànica Alcaloides Metathesis (Chemistry) Bioactive compounds Organic synthesis Alkaloids |
| title_short |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| title_full |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| title_fullStr |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| title_full_unstemmed |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| title_sort |
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings |
| dc.creator.none.fl_str_mv |
Díaz-Ruiz, Marina Urbina Teixidor, Aina Llor Brunés, Núria Bosch Cartes, Joan Amat Tusón, Mercedes Maseras Cuní, Feliu |
| author |
Díaz-Ruiz, Marina |
| author_facet |
Díaz-Ruiz, Marina Urbina Teixidor, Aina Llor Brunés, Núria Bosch Cartes, Joan Amat Tusón, Mercedes Maseras Cuní, Feliu |
| author_role |
author |
| author2 |
Urbina Teixidor, Aina Llor Brunés, Núria Bosch Cartes, Joan Amat Tusón, Mercedes Maseras Cuní, Feliu |
| author2_role |
author author author author author |
| dc.subject.none.fl_str_mv |
Metàtesi (Química) Compostos bioactius Síntesi orgànica Alcaloides Metathesis (Chemistry) Bioactive compounds Organic synthesis Alkaloids |
| topic |
Metàtesi (Química) Compostos bioactius Síntesi orgànica Alcaloides Metathesis (Chemistry) Bioactive compounds Organic synthesis Alkaloids |
| description |
In previous work we reported the formal synthesis of the marine macrolide (−)-callyspongiolide through a synthetic approach in which the generation of the key macrocyclic core relies on a ruthenium-catalyzed ring-closing metathesis reaction. However, besides the predicted macrolactone intermediate, an undesired cyclooctene was observed. We investigate here the mechanism of this critical step through density functional theory calculations. The results indicate that the chemoselectivity is not under kinetic control but ruled by thermodynamics. This conclusion is further confirmed by additional experimental studies. |
| publishDate |
2022 |
| dc.date.none.fl_str_mv |
2022 2023 2023 2024 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion |
| format |
article |
| status_str |
acceptedVersion |
| dc.identifier.none.fl_str_mv |
https://hdl.handle.net/2445/193700 |
| url |
https://hdl.handle.net/2445/193700 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
Versió postprint del document publicat a: https://doi.org/10.1016/j.tet.2022.133016 Tetrahedron, 2022 https://doi.org/10.1016/j.tet.2022.133016 |
| dc.rights.none.fl_str_mv |
cc-by-nc-nd (c) Elsevier B.V., 2022 https://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
cc-by-nc-nd (c) Elsevier B.V., 2022 https://creativecommons.org/licenses/by-nc-nd/4.0/ |
| eu_rights_str_mv |
openAccess |
| dc.format.none.fl_str_mv |
application/pdf |
| dc.publisher.none.fl_str_mv |
Elsevier B.V. |
| publisher.none.fl_str_mv |
Elsevier B.V. |
| dc.source.none.fl_str_mv |
Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica) reponame:Recercat. Dipósit de la Recerca de Catalunya instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
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Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
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Recercat. Dipósit de la Recerca de Catalunya |
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Recercat. Dipósit de la Recerca de Catalunya |
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15,812429 |