Unusual reductive coupling of alkynes and ketones: reactivity of titanacycles supported by dimethylsilylcalix[4]arene (DMSC) ligands

Oleg V. Ozerov, Carolyn P. Brock, Folami T. Ladipo

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Reaction of [(DMSC)Ti{1,2,4-(Me3Si)3C6H3}] (1) with 1 equiv of bipyridine (bpy) or 4,4′-dimethyl-2,2′-dipyridyl (dmbpy) and a slight excess of RC≡CH quantitatively produced [(DMSC)Ti(η2-RC≡CH)(L2)] (L2 = bpy or dmbpy) (5-16). (DMSC)TiPh2 (17) reacted with ≥2 equiv of bpy or dmbpy to give (DMSC)Ti(bpy)2 (18) and (DMSC)Ti(dmbpy)2 (19), respectively. Both 1H and 13C NMR data, as well as X-ray crystallography in the case of [(DMSC)Ti(η2-HC=CBut)(bpy)] (7), support exo-orientation of the alkyne's non-H substituent in 5-16. Reaction of [(DMSC)Ti{1,2,4-(Me3Si)3C6H3}] (1) with a mixture of RC≡CH and R2CO did not give the expected 5-oxa-1-titana-2-cyclopentene products but instead produced 2,7-dioxa-1-titana-4-cycloheptenes (20-25). The latter result may be understood in terms of the unique directing influence of the DMSC ligand.

Original languageEnglish
Pages (from-to)5016-5025
Number of pages10
JournalOrganometallics
Volume19
Issue number24
DOIs
StatePublished - Nov 27 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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