Rotational Spectra of Bicyclic Decanes: The Trans Conformation of (−)-Lupinine

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-12, Vol.117 (50), p.13673-13679
• Main Authors: Jahn, Michaela K, Dewald, David, Vallejo-López, Montserrat, Cocinero, Emilio J, Lesarri, Alberto, Grabow, Jens-Uwe
• Format: Article
• Language: English
• Subjects: Ab initio calculations; Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); Constants; Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Gages; Gauges; Hydrogen Bonding; Locks; Microwave spectroscopy; Models, Molecular; Molecular Conformation; Molecular properties and interactions with photons; Molecular spectra; Nitrogen atoms; Physics; Properties of molecules and molecular ions; Rotation; Rotation, vibration and vibration-rotation constants; Rotational; Rotational spectra; Sparteine - analogs & derivatives; Sparteine - chemistry; Stereoisomerism
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp407671m

The conformational and structural properties of the bicyclic quinolizidine alkaloid (−)-lupinine have been investigated in a supersonic jet expansion using microwave spectroscopy. The rotational spectrum is consistent with a single dominant trans conformation within a double-chair skeleton, which is stabilized by more than 10.4 kJ mol–1 with respect to other conformations. In the isolated conditions of the jet, the hydroxy methyl side chain of the molecule locks in to form an intramolecular O–H···N hydrogen bond to the electron lone pair at the nitrogen atom. Accurate rotational constants, centrifugal distortion corrections, and 14N nuclear quadrupole coupling parameters are reported and compared to ab initio (MP2) and DFT (M06-2X) calculations. The stability of lupinine is further compared computationally with epilupinine and decaline in order to gauge the influence of intramolecular hydrogen bonding, absent in these molecules.