Fomenting proton anisochronicity in the CH2D group

Benjamin D. Allen, Daniel J. O'Leary

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

A novel C-D⋯N interaction promotes an equilibrium isotope effect that causes a large chemical shift difference (43 ppb, 22 °C) for the diastereotopic methyl protons in the (N-CH2D)-(-)-isosparteinium cation. The observed chemical shift difference is in surprising agreement with a prediction of 44 ppb based upon an ab initio protocol. These calculations are also shown to reproduce the experimental shift difference in Anet's α-deutero-1,2-dimethylpiperidine (theory, 17 ppb; experiment, 14 ppb). The isosparteine-derived system described herein may provide an improved method for assigning the configuration and enantiomeric purity of stereogenic methyl groups (R-CHDT) by tritium NMR spectroscopy.

Original languageEnglish (US)
Pages (from-to)9018-9019
Number of pages2
JournalJournal of the American Chemical Society
Volume125
Issue number30
DOIs
StatePublished - Jul 30 2003

All Science Journal Classification (ASJC) codes

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

Fingerprint Dive into the research topics of 'Fomenting proton anisochronicity in the CH<sub>2</sub>D group'. Together they form a unique fingerprint.

  • Cite this