Increasing the structural span of alkyne metathesis

Peter Persich, Josep Llaveria, Rudy Lhermet, Teresa Deharo, Robert Stade, Azusa Kondoh, Alois Fürstner

Research output: Contribution to journalArticlepeer-review

62 Citations (Scopus)

Abstract

A new generation of alkyne metathesis catalysts, which are distinguished by high activity and an exquisite functional group tolerance, allows the scope of this transformation to be extended beyond its traditional range. They accept substrates that were previously found problematic or unreactive, such as propargyl alcohol derivatives, electron-deficient and electron-rich acetylenes of various types, and even terminal alkynes. Moreover, post-metathetic transformations other than semi-reduction increase the structural portfolio, as witnessed by the synthesis of a annulated phenol derivative via ring-closing alkyne metathesis (RCAM) followed by a transannular gold-catalyzed Conia-ene reaction. Further examples encompass a post-metathetic transannular ketone-alkyne cyclization with formation of a trisubstituted furan, a ruthenium-catalyzed redox isomerization, and a Meyer-Schuster rearrangement/oxa-Michael cascade. These reaction modes fueled model studies toward salicylate macrolides, furanocembranolides, and the cytotoxic macrolides acutiphycin and enigmazole A; moreover, they served as the key design elements of concise total syntheses of dehydrocurvularin (27) and the antibiotic agent A26771B (36). Ask for more! Many possibilities exist to take advantage of alkyne metathesis. In addition to the approved semi-reduction to stereodefined olefins, it is shown how to convert the products primarily formed into aromatic or heteroaromatic rings, enones, Michael adducts, or β-ketolactones. At the same time, new types of substrates were engaged, including electron-rich, electron-poor, and terminal alkynes, as well as propargyl alcohol derivatives.

Original languageEnglish
Pages (from-to)13047-13058
Number of pages12
JournalChemistry - A European Journal
Volume19
Issue number39
DOIs
Publication statusPublished - 2013 Sep 23
Externally publishedYes

Keywords

  • alkyne metathesis
  • gold
  • molybdenum
  • natural products
  • total synthesis
  • transannular reactions

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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