Strong influence of intramolecular Si⋯O proximity on reactivity: Systematic molecular structure, solvolysis, and mechanistic study of cyclic N-trimethylsilyl carboxamide derivatives

Roland Szalay, V. Harmat, János Eőri, Gábor Pongor

Research output: Contribution to journalArticle

Abstract

A comparative alcoholysis study of N-silylated derivatives of simple heterocyclic carboxamides (lactams, imides, ureas) is presented. The second-order rate constant values span a range as wide as three orders of magnitude. On the basis of DFT calculations, a good correlation between reactivity and the Si⋯O distance was found within each family of compounds. The viability of two different reaction pathways was evaluated using a detailed computational mechanistic study of the methanolysis of cyclic urea homologues. Peculiarities in the single-crystal X-ray diffraction structures of the trimethylsilyl and trimethylsiloxy phthalimides are also discussed.

Original languageEnglish
Pages (from-to)2186-2192
Number of pages7
JournalTetrahedron Letters
Volume58
Issue number23
DOIs
Publication statusPublished - Jan 1 2017

Keywords

  • Amide
  • DFT
  • Intramolecular
  • Reactivity
  • Silyl
  • Solvolysis

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Fingerprint Dive into the research topics of 'Strong influence of intramolecular Si⋯O proximity on reactivity: Systematic molecular structure, solvolysis, and mechanistic study of cyclic N-trimethylsilyl carboxamide derivatives'. Together they form a unique fingerprint.

  • Cite this