Acceleration of metallacycle-mediated alkyne–alkyne cross-coupling with TMSCl

James S. Cassidy, Haruki Mizoguchi, Glenn C. Micalizio

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Investigation of titanium-centered metallacycle-mediated cross-coupling between unsymmetrical internal alkynes has led to the discovery that TMSCl significantly accelerates the [Formula presented] bond forming event. We report a collection of results that compare the efficiency of this reaction employing Ti(Oi-Pr)4/2n-BuLi in PhMe with and without TMSCl, demonstrating in every case that the presence of TMSCl has a profound impact on efficiency. While relevant in the context of developing this fundamental bond-forming process as an entry to more complex organometallic transformations, these modified reaction conditions allow coupling processes to be run at >10 times the concentrations previously possible [in 2.4 M n-BuLi (hexanes)], without the requirement of additional solvent. Finally, we demonstrate the effectiveness of these modified reaction conditions for the annulative cross-coupling between TMS-alkynes and 1,6-enynes leading to the formation of angularly substituted hydrindanes with, now well appreciated, high levels of regio- and stereoselection.

Original languageEnglish
Pages (from-to)3848-3850
Number of pages3
JournalTetrahedron Letters
Volume57
Issue number34
DOIs
Publication statusPublished - Jan 1 2016
Externally publishedYes

Keywords

  • 1,3-Dienes
  • Directed reactions
  • Metallacycle-mediated cross-coupling
  • Titanium isopropoxide

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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