Impacts of Steric Compression, Protonation, and Intramolecular Hydrogen Bonding on the 15N NMR Spectroscopy of Norditerpenoid Alkaloids and Their Piperidine-Ring Analogues

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Abstract

1H-15N HMBC spectra of norditerpenoid alkaloids and their synthetic azabicyclic analogues were obtained to investigate the impacts of the through-space effect of steric compression, protonation, and formation of intramolecular hydrogen bonding on the 15N NMR spectroscopy of these natural products and their piperidine-containing analogues. A rare 15N NMR effect of steric compression is demonstrated in half-cage A/E-rings of norditerpenoid alkaloid free bases and their synthetic azabicyclic analogues, in which the distribution of the lone pair of electrons of the tertiary amine N-atom is sterically restricted by bridged cycloalkanes, e.g., cyclopentane, cyclohexane, and cycloheptane rings. This results in significant changes in the 15N chemical shift, typically by at least ∼10 ppm. The lone pair of electrons of the N-atom in the piperidine ring are sterically compressed whether the bridged cyclohexane ring adopts a chair or boat conformation. The 15N chemical shifts of 1α-OMe norditerpenoid alkaloid free bases significantly increase (ΔδN ≥ 15.6 ppm) on alkaloid protonation and thence the formation of an intramolecular hydrogen bond between N+-H and 1α-OMe. The intramolecular hydrogen bonds between the N-atom and 1α-OH of 1α-OH norditerpenoid alkaloid free bases, karacoline, condelphine, and neoline stabilize their A-rings, adopting an unusual twisted-boat conformation, and they also significantly increase δN of the tertiary amine N-atom.

Original languageEnglish
Pages (from-to)14116-14122
Number of pages7
JournalACS OMEGA
Volume5
Issue number23
Early online date8 Jun 2020
DOIs
Publication statusPublished - 16 Jun 2020

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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