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Landenberger P, Scheumann K, Keller M, et al. Pentagonal dodecahedranes: polyfunctionalization and MS fragmentation. J Org Chem. 2001;66(17):5744-58doi: 10.1021/jo010170+.
Landenberger, P., Scheumann, K., Keller, M., Hunkler, D., Fritz, H., Wörth, J., Knothe, L., & Prinzbach, H. (2001). Pentagonal dodecahedranes: polyfunctionalization and MS fragmentation. The Journal of organic chemistry, 66(17), 5744-58. https://doi.org/10.1021/jo010170+
Landenberger, P, et al. "Pentagonal dodecahedranes: polyfunctionalization and MS fragmentation." The Journal of organic chemistry vol. 66,17 (2001): 5744-58. doi: https://doi.org/10.1021/jo010170+
Landenberger P, Scheumann K, Keller M, Hunkler D, Fritz H, Wörth J, Knothe L, Prinzbach H. Pentagonal dodecahedranes: polyfunctionalization and MS fragmentation. J Org Chem. 2001 Aug 24;66(17):5744-58. doi: 10.1021/jo010170+. PMID: 11511248.
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J Org Chem. 2001 Aug 24;66(17):5744-58. doi: 10.1021/jo010170+.

Pentagonal dodecahedranes: polyfunctionalization and MS fragmentation.

The Journal of organic chemistry

P Landenberger, K Scheumann, M Keller, D Hunkler, H Fritz, J Wörth, L Knothe, H Prinzbach

Affiliations

  1. Chemisches Laboratorium der Universität Freiburg i. Br., Institut für Organische Chemie und Biochemie, Albertstrasse 21, D-79104 Freiburg i.Br., Germany.

PMID: 11511248 DOI: 10.1021/jo010170+

Abstract

With the use of four- to eight-fold functionalized dodecahedranes (1-3), opportunities to arrive at highly strained dodecahedranes with two to four pairs of vicinal, eclipsed bromine substituents through front-side substitution and addition reactions have been explored. In standard processes, the interception of beta-OCH(3) radical/cationic intermediates was not problematic (9-12, 37, 50). The interception of beta-CO(2)R radicals was possible for Cl(*) (18) but not for Br(*) (17). The interception of beta-chloro radicals was possible for Cl(*) (27) but not for Br(*) (26), and the interception of beta-Br cations ("bromonium ions") with Br(-) was modest (45) to highly inefficient (24, 26). Two X-ray structural analyses (dimethoxy dibromide 9 and tetramethoxy tetrabromide 53) indicated the structural consequences of the molecular strain introduced by the two (four) vicinal CH(3)O/Br pairs. A systematic analysis of the MS spectra confirms that, in virtually all cases studied, the elimination of the substituents occurs without significant carbon-cage disruption, leading ultimately to multiply unsaturated dodecahedral ions for dodecahedrahexa(C(20)H(8))enes, -hepta(C(20)H(6))enes, and -octa(C(20)H(4))enes.

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