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Two-Step Synthesis of Heptacyclo[6.6.0.0^2,6 .0^3,13 .0^4,11 .0^5,9 .0^10,14 ] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post-synthetic Functionalization.

ABSTRACT: A selective and scalable two-step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.0^2,6 .0^3,13 .0^4,11 .0^5,9 .0^10,14 ] 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.

SUBMITTER: Zielinski A

PROVIDER: S-EPMC7756769 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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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.

Zieliński Adam A Marset Xavier X Golz Christopher C Wolf Lawrence M LM Alcarazo Manuel M

Angewandte Chemie (International ed. in English) 20201015 51

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]-sigma ...[more]

PMID: 32881255

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