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Synthesis of Waixenicin A: Exploring Strategies for Nine-Membered Ring Formation.
Steinborn, Christian; Huber, Tatjana; Lichtenegger, Julian; Plangger, Immanuel; Höfler, Denis; Schnell, Simon D; Weisheit, Lara; Mayer, Peter; Wurst, Klaus; Magauer, Thomas.
Afiliación
  • Steinborn C; Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
  • Huber T; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany.
  • Lichtenegger J; Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
  • Plangger I; Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
  • Höfler D; Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
  • Schnell SD; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany.
  • Weisheit L; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany.
  • Mayer P; Department of Chemistry and Pharmacy, Ludwig-Maximilians-University Munich, Butenandtstrasse 5-13, 81377, Munich, Germany.
  • Wurst K; Institute of General, Inorganic & Theoretical Chemistry, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
  • Magauer T; Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria.
Chemistry ; 30(7): e202303489, 2024 Feb 01.
Article en En | MEDLINE | ID: mdl-37942708
We present a comprehensive account on our efforts behind the recently published synthesis of waixenicin A. Our approach for constructing the dihydropyran ring relied on an Achmatowicz rearrangement. For the assembly of the nine-membered ring, four distinct strategies were investigated. Our initial attempts using radical-based addition/fragmentation reactions targeting the C7-C11 bond proved unsuitable for accessing the 6/9-bicycle. By employing anionic fragmentation conditions at the furfuryl alcohol stage, we successfully reached a 5/9-bicycle. However, subsequent ring-expansion was unsuccessful. Alternative approaches, such as Nozaki-Hiyama-Kishi or Heck reactions to connect the C6-C7 bond, also encountered difficulties, with no nine-membered ring formation observed. Our first breakthrough came from our attempts to install the C5-C6 bond via an intramolecular alkylation. Surprisingly, subsequent functional group modifications proved unexpectedly challenging, necessitating a redesign of our synthetic route. Drawing from all our investigations, we concluded that construction of the C9-C10 bond would enable efficient nine-membered ring alkylation and would facilitate the installation of the desired substitution pattern along the southern periphery. Exploration of this strategy yielded further surprises but ultimately led to the successful synthesis of waixenicin A and 9-deacetoxy-14,15-deepoxyxeniculin. For the latter compound, a bioinspired one-step rearrangement to xeniafauranol A was achieved.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chemistry Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Austria Pais de publicación: Alemania
Texto completo
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XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chemistry Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Austria Pais de publicación: Alemania