Abstract
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.
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Gelalcha F. G., Bitterlich B., Anilkumar G., Tse M. K., Beller M., Angew. Chem. Int. Ed., 2007, 46(38), 7293
Urgoitia G., SanMartin R., Herrero M. T., Domínguez E., ACS Catal., 2017, 7(4), 3050
Tsuji J., Palladium Reagents and Catalysts: New Perspectives for the 21st Centure(First Edition), John Wiley & Sons, New York, 2004, 601
Baiju T. V., Gravel E., Doris E., Namboothiri I. N. N., Tetrahedron Lett., 2016, 57(36), 3993
Michel B. W., Sigman M. S., Aldrichimica Acta, 2011, 44(3), 55–62
Liu B., Jin F., Wang T., Yuan X., Han W., Angew. Chem., Int. Ed., 2017, 56(41), 12712
Zhang G., Hu X., Chiang C.-W., Yi H., Pei P., Singh A. K., Lei A., J. Am. Chem. Soc., 2016, 138(37), 12037
Zhang Z., Kumamoto Y., Hashiguchi T., Mamba T., Murayama H., Yamamoto E., Ishida T., Honma T., Tokunaga M., ChemSusChem, 2017, 10(17), 3482
Gao X., Zhou J., Peng X., Catal. Commun., 2019, 122, 73
Imbao J., van Bokhoven J. A., Clark A., Nachtegaal M., Nat. Commun., 2020, 11(1), 1118
Wang A., Li J., Zhang T., Nat. Rev. Chem., 2018, 2(6), 65
Cui X., Li W., Ryabchuk P., Junge K., Beller M., Nature Catalysis, 2018, 1 (6), 385
Zhang L., Ren Y., Liu W., Wang A., Zhang T., Natl. Sci. Rev., 2018, 5(5), 653
Yan H., Su C., He J., Chen W., J. Mater. Chem. A, 2018, 6(19), 8793
Li W.-H., Yang J., Jing H., Zhang J., Wang Y., Li J., Zhao J., Wang D., Li Y., J. Am. Chem. Soc., 2021, 143(37), 15453
Chen Z., Song J., Peng X., Xi S., Liu J., Zhou W., Li R., Ge R., Liu C., Xu H., Zhao X., Li H., Zhou X., Wang L., Li X., Zhong L., Rykov A. I., Wang J., Koh M. J., Loh K. P., Adv. Mater., 2021, 33(34), 2101382
Bakandritsos A., Kadam R. G., Kumar P., Zoppellaro G., Medved M., Tuček J., Montini T., Tomanec O., Andrýsková P., Drahoš B., Varma R. S., Otyepka M., Gawande M. B., Fornasiero P., Zbořil R., Adv. Mater., 2019, 31(17), 1900323
Vilé G., Di Liberto G., Tosoni S., Sivo A., Ruta V., Nachtegaal M., Clark A. H., Agnoli S., Zou Y., Savateev A., Antonietti M., Pacchioni G., ACS Catal., 2022, 12(5), 2947
Zhang Y., Ye S., Gao M., Li Y., Huang X., Song J., Cai H., Zhang Q., Zhang J., ACS Nano., 2022, 16(1), 1142
Chen Z., Liu J., Koh M. J., Loh K. P., Adv. Mater., 2021, 33, 2103882
Li W.-H., Yang J., Wang D., Li Y., Chem, 2022, 8(1), 119
Li F., Han G.-F., Noh H.-J., Kim S.-J., Lu Y., Jeong H. Y., Fu Z., Baek J.-B., Energy Environ. Sci., 2018, 11(8), 2263
Isbrandt E. S., Sullivan R. J., Newman S. G., Angew. Chem., Int. Ed., 2019, 58(22), 7180
Tang X., Wu W., Zeng W., Jiang H., Acc. Chem. Res., 2018, 51(5), 1092
Zhan M., Zhang T., Huang H., Xie Y., Chen Y., J. Labelled Compd. Rad., 2014, 57(8), 533
Mimoun H., Charpentier R., Mitschler A., Fischer J., Weiss R., J. Am. Chem. Soc., 1980, 102(3), 1047
Acknowledgements
This work was supported by the National Research Foundation, Prime Minister’s Office, Singapore(No.NRF-CRP16-2015-02). We thank Prof. LIU Cuibo at Tianjin University and Prof. KOH Ming Joo at National University of Singapore for data collection and insightful discussions. We appreciate Prof. ZHAO Xiaoxu at Peking University for the STEM characterization and data analysis, as well as Dr. XI Shibo at Singapore Synchrotron Light Source for XAS measurements and data processing.
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Song, J., Liu, J., Loh, K.P. et al. Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation. Chem. Res. Chin. Univ. 38, 1239–1242 (2022). https://doi.org/10.1007/s40242-022-2130-x
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DOI: https://doi.org/10.1007/s40242-022-2130-x