Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates

A straightforward phosphine‐catalyzed formal [4+2] annulation between α‐branched allenoates and arylidene azlactones has been developed to access highly functionalized spirocyclohexenes. This cyclization favors the γ‐addition of the phosphine‐activated allenoates over a β′‐addition pathway. Detailed...

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Detalles Bibliográficos
Autores principales: Eitzinger, Andreas, Zielke, Katharina, Widhalm, Michael, Robiette, Raphaël, Waser, Mario
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2018
Materias:
Full Papers
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6114148/
https://www.ncbi.nlm.nih.gov/pubmed/30175031
http://dx.doi.org/10.1002/ajoc.201800275
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author Eitzinger, Andreas
Zielke, Katharina
Widhalm, Michael
Robiette, Raphaël
Waser, Mario
author_facet Eitzinger, Andreas
Zielke, Katharina
Widhalm, Michael
Robiette, Raphaël
Waser, Mario
author_sort Eitzinger, Andreas
collection PubMed
description A straightforward phosphine‐catalyzed formal [4+2] annulation between α‐branched allenoates and arylidene azlactones has been developed to access highly functionalized spirocyclohexenes. This cyclization favors the γ‐addition of the phosphine‐activated allenoates over a β′‐addition pathway. Detailed computational studies support the proposed mechanism and provide a reasonable explanation for the observed regioselectivity and the noted effect of the catalyst.
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spelling pubmed-61141482018-08-29 Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates Eitzinger, Andreas Zielke, Katharina Widhalm, Michael Robiette, Raphaël Waser, Mario Asian J Org Chem Full Papers A straightforward phosphine‐catalyzed formal [4+2] annulation between α‐branched allenoates and arylidene azlactones has been developed to access highly functionalized spirocyclohexenes. This cyclization favors the γ‐addition of the phosphine‐activated allenoates over a β′‐addition pathway. Detailed computational studies support the proposed mechanism and provide a reasonable explanation for the observed regioselectivity and the noted effect of the catalyst. John Wiley and Sons Inc. 2018-06-10 2018-08 /pmc/articles/PMC6114148/ /pubmed/30175031 http://dx.doi.org/10.1002/ajoc.201800275 Text en © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Eitzinger, Andreas
Zielke, Katharina
Widhalm, Michael
Robiette, Raphaël
Waser, Mario
Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates
title Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates
title_full Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates
title_fullStr Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates
title_full_unstemmed Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates
title_short Syntheses of Highly Functionalized Spirocyclohexenes by Formal [4+2] Annulation of Arylidene Azlactones with Allenoates
title_sort syntheses of highly functionalized spirocyclohexenes by formal [4+2] annulation of arylidene azlactones with allenoates
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6114148/
https://www.ncbi.nlm.nih.gov/pubmed/30175031
http://dx.doi.org/10.1002/ajoc.201800275
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