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

Fingerprint

Alkynes
Hexanes
Organometallics
Titanium
n-butyllithium
hydrindane
n-hexane
polyurethane-polypropylene composite

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Acceleration of metallacycle-mediated alkyne–alkyne cross-coupling with TMSCl. / Cassidy, James S.; Mizoguchi, Haruki; Micalizio, Glenn C.

In: Tetrahedron Letters, Vol. 57, No. 34, 01.01.2016, p. 3848-3850.

Research output: Contribution to journalArticle

Cassidy, James S. ; Mizoguchi, Haruki ; Micalizio, Glenn C. / Acceleration of metallacycle-mediated alkyne–alkyne cross-coupling with TMSCl. In: Tetrahedron Letters. 2016 ; Vol. 57, No. 34. pp. 3848-3850.
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