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dc.creatorEcija, Patriciaen_US
dc.creatorCocinero, Emilio J.en_US
dc.creatorBasterretxea, Francisco J.en_US
dc.creatorFernandez, Jose A.en_US
dc.creatorCastano, Fernandoen_US
dc.creatorLesarri, Albertoen_US
dc.date.accessioned2013-07-16T21:48:01Z
dc.date.available2013-07-16T21:48:01Z
dc.date.issued2013en_US
dc.identifier2013-MH-03en_US
dc.identifier.urihttp://hdl.handle.net/1811/55613
dc.descriptionAuthor Institution: Departamento de Quimica Fisica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco (UPV/EHU), Ap.644, E-48940, Bilbao, Spain; Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Spainen_US
dc.description.abstractTropane alkaloids have diverse pharmacological uses and are well-known for their neurostimulant activity. Previous structure-activity-relationship established correlations between bioactivity and several aspects of ligand conformation and stereochemistry, including delicate intramolecular effects like nitrogen inversion$^{a}$. We have initiated a series of structural studies on tropane alkaloids$^{b}$, aimed to discerning their intrinsic stereochemical properties using rotational spectroscopy in supersonic jets$^{c}$. Here we extend these studies to the epoxytropanes, initially motivated to interrogate the influence of the epoxy group on nitrogen inversion and ring conformation. The rotational spectrum evidences a single structure in the gas phase, providing a first description of the (three ring) structurally-distorted tropane in scopoline. The determined rotational parameters of scopoline reveal the structural consequences of the intramolecular cyclation of scopine, which breaks the original epoxy group and creates a new ether bridge and a 7$\beta$-hydroxytropane configuration. The hydroxyl group further stabilizes the molecule by an $O-H \cdots N$ intramolecular hydrogen bond, which, in turn, forces the N-methyl group to the less stable axial form$^{b}$. The experimental work was supported by ab initio and DFT calculations.\\ $^{a}$ i) S.Singh, \emph{Chem. Rev.} 100, 925 (2000); ii) A. Krunic, D. Pan, W.J. Dunn III, S.V.S. Miariappan, \emph{Bioorg. & Med. Chem.} 17, 811 (2009).\\ $^{b}$ E.J. Cocinero, A. Lesarri, P. Ecija, J.-U. Grabow, J.A. Fernandez, F. Casta\~{n}o, \emph{Phys. Chem. Chem. Phys.} 12, 6076 (2010).\\ $^{c}$ E.J. Cocinero, A. Lesarri, P. Ecija, J.-U. Grabow, J.A. Fernandez, F. Casta\~{n}o, \emph{Phys. Chem. Chem. Phys.} 12, 12486 (2010).en_US
dc.language.isoenen_US
dc.publisherOhio State Universityen_US
dc.titleMW SYSTEMATIC STUDY OF ALKALOIDS: THE DISTORTED TROPANE OF SCOPOLINEen_US
dc.typeArticleen_US
dc.typeImageen_US
dc.typePresentationen_US


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