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Highly Strained Tertiary sp3 Scaffolds: Synthesis of Functionalized Cubanes and Exploration of Their Reactivity under Pd(II) Catalysis

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School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland
*E-mail: [email protected] (M.O.S.).
Cite this: Organometallics 2015, 34, 7, 1408–1414
Publication Date (Web):March 31, 2015
https://doi.org/10.1021/acs.organomet.5b00151
Copyright © 2015 American Chemical Society
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    Abstract

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    A series of chemically distinct, highly strained, activated cubane scaffolds were synthesized through optimization of the metal–halogen exchange reactions of iodinated cubane derivatives. This included the first reported successful attachment of both boron and phosphorus, key elements in potential transition-metal-catalyzed cross-coupling reactions, on the cubane scaffold. Additionally, Zn, Sn, Si, S, and various C-based systems were also attached in a high-yielding, one-pot reaction from readily available precursors. A comprehensive program investigating the reactivity of these tertiary cubane nucleophiles toward Suzuki–Miyaura, Negishi, and Stille cross-coupling methods, never previously reported with the cubane scaffold, is also described, but proved unsuccessful.

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    Comprehensive details regarding the transition-metal catalyzed reactions attempted with 11–14 together with spectral data for all new compounds are provided. This material is available free of charge via the Internet at http://pubs.acs.org. CCDC 1044128 (15b) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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