Synthesis, structure, and chemistry of new, mixed group 14 and 16 heterocycles: Nucleophile-induced ring contraction of mesocyclic dications

Eric Block, Evgeny V. Dikarev, Richard S. Glass, Jin Jin, Bo Li, Xiaojie Li, Shao Zhong Zhang

Research output: Contribution to journalArticlepeer-review

42 Scopus citations

Abstract

More than 40 new 4- to 12-membered ring heterocycles containing various combinations of Group 14 and 16 elements Si, Sn, S, Se, and Te have been synthesized and fully characterized. Synthesis of these small-ring as well as medium-ring (mesocyclic) heterocycles from α,ω-dihalides is facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the precursors. Conformations of several of the new ring systems in the solid state have been determined by X-ray crystal structure analysis. Oxidation of mixed S(Se, Te)/Si eight-membered ring mesocycles with NOPF6 or Br2 gives dications or a bicyclic dibromide, respectively, which can be characterized by NMR methods. On treatment with nucleophiles, mesocyclic dications, or the corresponding radical cations undergo ring contraction, giving five- or six-membered ring heterocycles. Photolysis of a S/Se four-membered ring heterocycle gives selenoformaldehyde, trapped in 80% yield with 2,3-dimethyl-1,3-butadiene.

Original languageEnglish (US)
Pages (from-to)14949-14961
Number of pages13
JournalJournal of the American Chemical Society
Volume128
Issue number46
DOIs
StatePublished - Nov 22 2006

ASJC Scopus subject areas

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

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