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Palladium-catalysed norbornene-mediated C–H functionalization of arenes

Nature Chemistry volume 7, pages 863–870 (2015)Cite this article

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Abstract

The Catellani reaction — a palladium-catalysed C–H functionalization reaction mediated by norbornene — was first reported in 1997. The capacity to functionalize both the ortho and ipso positions of aryl halides in a single transformation held great appeal. We reported an annulative Catellani reaction in 2000. Since then, our two groups have explored the synthetic utility of this reaction and dramatic progress has been made by a number of groups in the past five years. Whereas the original Catellani reaction uses Pd(0) catalysts, recent studies have shown that Pd(II) catalysts can be used in combination with norbornene to effect (1) direct 2-alkylation of indoles and pyrroles and (2) selective meta-C–H functionalization of arenes bearing commonly used ortho-directing groups, thereby opening new avenues for future research. We describe the most recent developments concerning the Pd-catalysed norbornene-mediated C–H functionalization of arenes, including applications in natural products synthesis. We outline challenges and future opportunities.

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Figure 1: Early developments and recent examples of the Pd(0)-catalysed ortho-C–H amination of aryl iodides.
Figure 2: Cascade reactions provide access to chiral helical alkenes.
Figure 3: Pd(ii)-catalysed norbornene-mediated C–H functionalization of arenes.
Figure 4: Recent examples of natural products synthesis using a Catellani-type reaction as the key step.

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Acknowledgements

We thank the Natural Sciences and Engineering Research Council (NSERC), Merck, Merck Frosst, the University of Toronto and Alphora Research Inc. for financial support. M.L. thanks the Canada Council for the Arts for a Killam Fellowship. We also thank D. A. Petrone for his enormous help during the preparation of this manuscript.

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  1. Department of Chemistry, Davenport Laboratories, University of Toronto, 80 St George Street, Toronto, M5S 3H6, Ontario, Canada

    Juntao Ye & Mark Lautens

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Correspondence to Mark Lautens.

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Ye, J., Lautens, M. Palladium-catalysed norbornene-mediated C–H functionalization of arenes. Nature Chem 7, 863–870 (2015). https://doi.org/10.1038/nchem.2372

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