Abstract
Reactions with the unstable and highly reactive zwitterionic intermediates generated in processes catalysed by transition metals are providing new opportunities for molecular constructions. Insertion reactions involve the collapse of zwitterionic intermediates, but trapping them would allow structural elaborations that are not currently available. To synthesize complex molecules in this manner, reactive electrophiles can be used to trap the zwitterionic intermediates. Here, we describe the use of imines, activated by chiral organocatalysts, and a highly efficient integrated rhodium and chiral Brønsted acid co-catalysed process to trap zwitterionic intermediates that have been proposed previously to undergo a formal C–H insertion reaction, allowing us to obtain polyfunctionalized indole and oxindole derivatives in a single step with excellent diastereoselectivity and enantioselectivity.
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Change history
14 August 2012
In the version of this Article previously published online, in Table 3, Entry 1, the structure of compound 6b was missing a Br atom label. This has now been corrected in all versions of this Article.
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Acknowledgements
The authors acknowledge support from the National Science Foundation of China (nos 20932003 and 21125209 to W.-H.H.), the MOST of China (2011CB808600) and from Shanghai (10XD1401700). M.P.D. thanks the National Institutes of Health (GM 46503) and National Science Foundation (CHE-0748121) for financial support.
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Contributions
H.Q. and M.L. contributed equally to the work. H.Q. designed and performed experiments for the three-component reaction, and M.L. designed and performed experiments for oxindole formation. L.-Q.J. took part in the development of the initial reaction. F.-P.L. made the organocatalysts. L.Z. and C.-W.Z. performed experiments. M.P.D. discussed, commented on and revised the manuscript. W.-H.H. conceived and directed the project. W.-H.H., M.L. and H.Q. wrote the paper.
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Crystallographic data for compound 5ba (CIF 28 kb)
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Crystallographic data for compound 6b (CIF 20 kb)
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Qiu, H., Li, M., Jiang, LQ. et al. Highly enantioselective trapping of zwitterionic intermediates by imines. Nature Chem 4, 733–738 (2012). https://doi.org/10.1038/nchem.1406
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DOI: https://doi.org/10.1038/nchem.1406
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