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Manganese-catalysed divergent silylation of alkenes

Nature Chemistry volume 13, pages 182–190 (2021)Cite this article

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Abstract

Transition-metal-catalysed, redox-neutral dehydrosilylation of alkenes is a long-standing challenge in organic synthesis, with current methods suffering from low selectivity and narrow scope. In this study, we report a general and simple method for the manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, with Mn2(CO)10 as a catalyst precursor, by using a ligand-tuned metalloradical reactivity strategy. This enables versatility and controllable selectivity with a 1:1 ratio of alkenes and silanes, and the synthetic robustness and practicality of this method are demonstrated using complex alkenes and light olefins. The selectivity of the reaction has been studied using density functional theory calculations, showing the use of an iPrPNP ligand to favour dehydrosilylation, while a JackiePhos ligand favours hydrosilylation. The reaction is redox-neutral and atom-economical, exhibits a broad substrate scope and excellent functional group tolerance, and is suitable for various synthetic applications on a gram scale.

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Fig. 1: The state of the art for divergent silylation of alkenes.
Fig. 2: Preliminary mechanistic studies.
Fig. 3: Mechanistic proposal and DFT studies.
Fig. 4: Enrichment and elaboration of products.

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Data availability

All data generated or analysed during this study are included in this Article and its Supplementary Information. Crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (CCDC) as CCDC 1937151 (5), 1937156 (6) and 1937154 (19) and can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/getstructures.

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Acknowledgements

We thank the National Natural Science Foundation of China (grants 21971108, 21971111, 21702098, 21703118, 21732003 and 21672099), the Fundamental Research Funds for the Central Universities (020514380214), the Natural Science Foundation of Jiangsu Province (grant no. BK20190006), the ‘Innovation & Entrepreneurship Talents Plan’ of Jiangsu Province, the ‘Jiangsu Six Peak Talent Project’, Shandong Provincial Natural Science Foundation (grant no. ZR2017MB038) and start-up funds from Nanjing University for financial support. Y. Liang, G. Wang and J. Han are acknowledged for their helpful suggestions and discussions. X. Wu and Y. Zhao are acknowledged for their help with H2 liberation reactions and X-ray single-crystal structure determination. We also thank K. Liu, Z. Yan, Y. Ning and W. Li for reproducing products 3a, 3v, 4a and 4m and C. Zhu, J. Han, Y. Pang, S. Fang and W. Li for their help with the preparation of this manuscript. The DFT calculations were supported by the High Performance Computing Center of Qufu Normal University.

Author information

Author notes

  1. These authors contributed equally: Jie Dong, Xiang-Ai Yuan, Zhongfei Yan, Liying Mu.

Authors and Affiliations

  1. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

    Jie Dong, Zhongfei Yan, Junyang Ma, Chengjian Zhu & Jin Xie

  2. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, China

    Xiang-Ai Yuan & Liying Mu

  3. College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, China

    Zhongfei Yan

  4. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, China

    Chengjian Zhu

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Contributions

J.D., Z.Y. and J.X. conceived and designed the experiments. J.D., Z.Y. and J.M. performed the experiments. J.D. and Z.Y. analysed and discussed the experimental data. X.-A.Y. and L.M. performed DFT calculations and discussed the manuscript. J.X. wrote the manuscript with input from all authors and discussed with C.Z. All the authors have approved the final version of the manuscript.

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Correspondence to Jin Xie.

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Supplementary information

Supplementary Information

Supplementary Tables 1–8, Figs. 1–30, Methods, text, experimental information, NMR, IR, GC-MS, HPLC spectra and references.

Supplementary Data 1

Crystallographic data for compound 5. CCDC reference 1937151.

Supplementary Data 2

Crystallographic data for compound 6. CCDC reference 1937156.

Supplementary Data 3

Crystallographic data for compound 19. CCDC reference 1937154.

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Dong, J., Yuan, XA., Yan, Z. et al. Manganese-catalysed divergent silylation of alkenes. Nat. Chem. 13, 182–190 (2021). https://doi.org/10.1038/s41557-020-00589-8

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