Synthesis of Angularly Substituted trans-Fused Decalins through a Metallacycle-Mediated Annulative Cross-Coupling Cascade

Haruki Mizoguchi, Glenn C. Micalizio

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

A convergent coupling reaction is described that enables the stereoselective construction of angularly substituted trans-fused decalins from acyclic precursors. The process builds on our alkoxide-directed titanium-mediated alkyne–alkyne coupling and employs a 1,7-enyne coupling partner. Overall, the reaction is thought to proceed through initial formation of a tetrasusbstituted metallacyclopentadiene, stereoselective intramolecular [4+2] cycloaddition, elimination, isomerization, and regio- and stereoselective protonation. Distinct from our early studies directed at the synthesis of trans-fused hydrindanes, the current annulative coupling reveals an important effect of TMSCl in controlling the final protonation—the event that establishes the stereochemistry of the ring fusion.

Original languageEnglish
Pages (from-to)13099-13103
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number42
DOIs
Publication statusPublished - 2016

Keywords

  • Diels–Alder reactions
  • carbocycles
  • cascade reactions
  • cross-coupling
  • cycloadditions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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