Nucleophilic additions of trimethylsilyl cyanide to cyclic oxocarbenium ions: Evidence for the loss of stereoselectivity at the limits of diffusion control

Siddhartha R. Shenoy, Deborah M. Smith, K. A. Woerpel

Research output: Contribution to journalArticle

Abstract

The limitations of stereoelectronic models in assessing the stereoselective nucleophilic substitution reactions of cyclic oxocarbenium ions at high reaction rates are discussed. Evidence is provided suggesting that the diastereoselectivity of nucleophilic substitution reactions is attenuated at the limits of diffusion control. The low diastereoselectivities observed in the reactions of trimethylsilyl cyanide with five- and six-membered ring oxocarbenium ions are attributed to the high reactivity of the nucleophile and its reactions with these electrophiles at diffusion control rates.

Original languageEnglish (US)
Pages (from-to)8671-8677
Number of pages7
JournalJournal of the American Chemical Society
Volume128
Issue number26
DOIs
StatePublished - Jul 5 2006

ASJC Scopus subject areas

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

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