Indium-mediated β-allylation, β-propargylation, and β-allenylation onto α,β-unsaturated ketones: Reactions of in-situ-generated 3-tert-butyldimethylsilyloxyalk-2-enylsulfonium salts with in-situ-generated organoindium reagents

Kooyeon Lee, Hyunseok Kim, Tomoya Miura, Koichi Kiyota, Hiroyuki Kusama, Sunggak Kim, Nobuharu Iwasawa, Phil Ho Lee

Research output: Contribution to journalArticlepeer-review

39 Citations (Scopus)

Abstract

3-tert-Butyldimethylsilyloxyalk-2-enylsulfonium salts, generated in situ from the reaction of α,β-enones with dimethyl sulfide in the presence of TBSOTf, underwent a novel nucleophilic substitution with allylindiums to give silyl enol ethers of δ,ε-alkenyl ketones in good yields, which correspond to formal Michael addition products. In a similar manner, 1,4-propargylation of propargylindiums onto the sulfonium salts produced the corresponding silyl enol ethers of δ,ε-alkynyl ketones in good yields. Organoindium reagents derived from γ-substituted propargyl bromide and indium afforded the corresponding silyl enol ethers of β-allenyl ketones in good yields. The reaction proceeds via an addition-substitution mechanism involving the formation of allylic sulfonium salts. The presence of the intermediate sulfonium salt was confirmed by observation of the low-temperature 1H NMR spectra.

Original languageEnglish
Pages (from-to)9682-9688
Number of pages7
JournalJournal of the American Chemical Society
Volume125
Issue number32
DOIs
Publication statusPublished - Aug 13 2003
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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