Synthetic Entry to Polyfunctionalized Molecules through the [3+2]-Cycloaddition of Thiocarbonyl Ylides

  • J Am Chem Soc. 2019 Aug 28;141(34):13352-13357. doi: 10.1021/jacs.9b07729.
Franz-Lucas Haut  1 ,  Christoph Habiger  1 ,  Klaus Speck  2 ,  Klaus Wurst  3 ,  Peter Mayer  2 ,  Johannes Nepomuk Korber  2 ,  Thomas Müller  1 ,  Thomas Magauer  1
Affiliations
  • 1. Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck , Innrain 80-82 , 6020 Innsbruck , Austria.
  • 2. Department of Chemistry and Pharmacy , Ludwig-Maximilians-University Munich , Butenandtstrasse 5-13 , 81377 Munich , Germany.
  • 3. Institute of General, Inorganic & Theoretical Chemistry, Leopold-Franzens-University Innsbruck , Innrain 80-82 , 6020 Innsbruck , Austria.
PMID: 31408334 DOI: 10.1021/jacs.9b07729
Abstract

Here we present a comprehensive study on the [3+2]-cycloaddition of thiocarbonyl ylides with a wide variety of alkenes and alkynes. The obtained dihydro- and tetrahydrothiophene products serve as exceptionally versatile intermediates providing access to thiophenes, dienes, dendralenes, and vic-quarternary carbon centers. The use of high-pressure conditions enables thermally unstable, sterically encumbered or moderately reactive substrates to undergo the cycloaddition under mild conditions, thereby increasing the yield by up to 58%. In addition, we showcase its utility by the formal syntheses of the pharmaceuticals NGB 4420 and tenilapine.

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