Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage

Cristina García-Simón, Rafael Gramage-Doria, Saeed Raoufmoghaddam, Teodor Parella, Miquel Costas, Xavi Ribas, Joost N.H. Reek

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    93 Citations (Scopus)

    Abstract

    © 2015 American Chemical Society. Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules.
    Original languageEnglish
    Pages (from-to)2680-2687
    JournalJournal of the American Chemical Society
    Volume137
    Issue number7
    DOIs
    Publication statusPublished - 25 Feb 2015

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    García-Simón, C., Gramage-Doria, R., Raoufmoghaddam, S., Parella, T., Costas, M., Ribas, X., & Reek, J. N. H. (2015). Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage. Journal of the American Chemical Society, 137(7), 2680-2687. https://doi.org/10.1021/ja512637k