Details
| Original language | English |
|---|---|
| Pages (from-to) | 13673-13679 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry A |
| Volume | 117 |
| Issue number | 50 |
| Publication status | Published - 19 Dec 2013 |
Abstract
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-HN 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.
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Journal of Physical Chemistry A, Vol. 117, No. 50, 19.12.2013, p. 13673-13679.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Rotational spectra of bicyclic decanes
T2 - The trans conformation of (-)-lupinine
AU - Jahn, Michaela K.
AU - Dewald, David
AU - Vallejo-López, Montserrat
AU - Cocinero, Emilio J.
AU - Lesarri, Alberto
AU - Grabow, Jens Uwe
PY - 2013/12/19
Y1 - 2013/12/19
N2 - 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-HN 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.
AB - 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-HN 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.
UR - http://www.scopus.com/inward/record.url?scp=84890929810&partnerID=8YFLogxK
U2 - 10.1021/jp407671m
DO - 10.1021/jp407671m
M3 - Article
C2 - 24028578
AN - SCOPUS:84890929810
VL - 117
SP - 13673
EP - 13679
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 50
ER -