Two-Step Synthesis of Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post-synthetic Functionalization |
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| Authors: | Adam Zieliński Dr. Xavier Marset Dr. Christopher Golz Prof. Dr. Lawrence M. Wolf Prof. Dr. Manuel Alcarazo |
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| Affiliation: | 1. Institut für Organische und Biomolekulare Chemie, Georg August Universität Göttingen, Tammannstr 2, 37077 Göttingen, Germany These authors contributed equally to this work.;2. Institut für Organische und Biomolekulare Chemie, Georg August Universität Göttingen, Tammannstr 2, 37077 Göttingen, Germany;3. Department of Chemistry, University of Massachusetts Lowell, Lowell, MA, 01854 USA |
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| Abstract: | A selective and scalable two-step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh-catalyzed stepwise homo Diels–Alder cyclisation of NBD into its exo-cis-endo dimer. Treatment of this compound with acid promotes its evolution to HCTD via a [1,2]-sigmatropic rearrangement. The assemblies of 7,12-disubstituted cages from 7-(alkyl/aryl) NBDs, as well as the selective post-synthetic C−H functionalization of the core HCTD scaffold at position C1, or positions C1 and C4 are described. |
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| Keywords: | cage compounds cationic ligands C−H functionalization HCTD homo Diels–Alder |
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