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

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Molecular Structure
Molecular structure
Urea
Phthalimides
Imides
Derivatives
Lactams
Discrete Fourier transforms
X-Ray Diffraction
Rate constants
Single crystals
X ray diffraction

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Strong influence of intramolecular Si⋯O proximity on reactivity : Systematic molecular structure, solvolysis, and mechanistic study of cyclic N-trimethylsilyl carboxamide derivatives. / Szalay, Roland; Harmat, V.; Eőri, János; Pongor, Gábor.

In: Tetrahedron Letters, Vol. 58, No. 23, 01.01.2017, p. 2186-2192.

Research output: Contribution to journalArticle

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