Abstract
Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C–O bonds. Achieving site-selective functionalization of alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report a strategy for selective carbenoid O–H insertion that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities for organic transformations by merging material science and catalysis. This catalytic protocol delivers excellent selectivities (up to 99:1) for the functionalization of aliphatic over phenolic O–H bonds, whereas the analogous homogeneous catalyst, Ir(ttp)COCl (ttp = 5,10,15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest that the site-selectivity derives from the lower oxidation state of the iridium metal centre in the heterogeneous catalyst and its impact on the absorption energies of the reactants. These results showcase an example of a heterogeneous single-atom catalyst providing superior site-selectivity and provide a complementary strategy to address challenges in catalysis for organic synthesis.
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Data relating to the characterization data of materials (TEM, STEM, XANES, EXAFS, XPS, X-ray diffraction), general methods, experimental procedures, mechanistic studies, DFT computational studies, mass spectrometry and NMR spectra are available in the Supplementary Information or from the corresponding authors upon reasonable reuqest.
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Acknowledgements
J.Z. acknowledges support from the Shanghai Municipal Science and Technology Major Project (2018SHZDZX03) and the Program of Introducing Talents of Discipline to Universities (B16017). S.J., D.W. and Y L. acknowledge the National Key R&D Program of China (2018YFA0702003) and the National Natural Science Foundation of China (21890383). They thank the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF). J.D. acknowledges the Youth Innovation Promotion Association of Chinese Academy of Sciences (2018017). F.D.T. acknowledges support by the Director, Office of Science, Office of Basic Energy Science and the Division of Chemical Sciences, Geosciences, and Bioscience of the US Department of Energy at Lawrence Berkeley National Laboratory (grant DE-AC0205CH1123). We thank B. Ye from ShanghaiTech University for helpful discussions.
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J.Z., S.J. and P.G. performed most of the experiments, analysed the experimental data and co-wrote the paper. C.G. performed computational studies, analysed the computational data and co-wrote the paper. H.L. and J.D. helped to collect and analyse the XAFS data. J.Z., D.W., Y.L. and F.D.T. designed and guided the research, and co-wrote the paper. All the authors discussed the results and contributed to writing the manuscript.
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Zhao, J., Ji, S., Guo, C. et al. A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion. Nat Catal 4, 523–531 (2021). https://doi.org/10.1038/s41929-021-00637-7
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DOI: https://doi.org/10.1038/s41929-021-00637-7
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