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  • Review Article
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Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization

Nature Reviews Chemistry volume 3, pages 347–360 (2019)Cite this article

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Abstract

C–H functionalization has become widely recognized as an exciting new strategy for the synthesis of complex molecular targets. Instead of relying on functional groups as the controlling elements of how molecules are assembled, this strategy offers an altogether different logic for organic synthesis. For this type of strategy to be successful, reagents and catalysts need to be developed that generate intermediates that are sufficiently reactive to functionalize C–H bonds but are still capable of distinguishing between the many different C–H bonds and other functional groups present in a molecule. The most well-established approaches have tended to use substrates that inherently have a favoured site for C–H functionalization or rely on intramolecular reactions to control where the reaction will occur. A challenging but potentially more versatile approach would be to use catalysts to control the site selectivity without requiring the influence of any directing group. One example that is capable of achieving such transformations is the C–H insertion chemistry of transient metal carbenes. Dirhodium tetracarboxylates have been shown to be especially effective catalysts for these reactions. This Review highlights the development of these dirhodium catalysts and illustrates their effectiveness to control both site-selective and stereoselective C–H functionalization of a wide variety of substrates.

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Fig. 1: Strategies for site-selective C–H functionalization.
Fig. 2: Carbene-induced C–H insertion with diazoacetates.
Fig. 3: Rhodium-catalysed C–H functionalization with donor/acceptor carbenes.
Fig. 4: C–H functionalization as a strategy in organic synthesis.
Fig. 5: Chiral dirhodium catalysts for intermolecular C–H functionalization.
Fig. 6: Catalyst-controlled site-selective C–H functionalization.
Fig. 7: Selective functionalization of unactivated C–H bonds.
Fig. 8: Desymmetrization of alkyl-substituted cycloalkanes.
Fig. 9: Streamlined synthesis by sequential C–H functionalization reactions.

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Acknowledgements

Financial support was provided by the US National Science Foundation under the Center for Chemical Innovation, Center for Selective C–H Functionalization (CHE-1700982). Catalyst 55 was initially developed with financial support provided by the US National Institutes of Health (GM-099142).

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Nature Reviews Chemistry thanks E. Alexanian and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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  1. Department of Chemistry, Emory University, Atlanta, GA, USA

    Huw M. L. Davies & Kuangbiao Liao

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K.L. and H.M.L.D. both contributed to all steps of manuscript preparation and writing.

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Correspondence to Huw M. L. Davies.

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H.M.L.D. is a named inventor on a patent entitled Dirhodium Catalyst Compositions and Synthetic Processes Related Thereto (US 8,974,428, issued 10 March 2015). K.L. has no competing interests.

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Davies, H.M.L., Liao, K. Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization. Nat Rev Chem 3, 347–360 (2019). https://doi.org/10.1038/s41570-019-0099-x

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