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Theoretical insight into the activity and selectivity in palladium/Ming-Phos-catalyzed three-component asymmetric synthesis of gem-diarylmethine silanes

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Abstract

Recently, a three-component coupling reaction for efficient construction of gem-diarylmethine silanes was developed, utilizing a Pd-Ming-Phos catalyst. To explore the underlying mechanism governing this intriguing reaction, we have conducted comprehensive density functional theory (DFT) computations (M06-L/SDD/6-311++G(d,p)/SMD//B3LYP-D3/lanl2dz/6-31G(d,p)). DFT calculations reveal that the oxidative addition of ArBr to Pd(0) is the rate-determining step, and the carbenation process of PhCHN2 to Pd(II) is the enantioselectivity-determining step. Moreover, the Ming-Phos ligand exhibits a self-adaptive nature, allowing it to dynamically adapt its coordination patterns with the metal center in different elementary steps, thereby enhancing the overall reactivity. The enantioselectivity is determined by both the trans effect and the side-arm effect of the ligand. This mechanism nicely explains why TY-Phos with P-tBu2 instead of the Ming-Phos with P-Ph2 results in poor reactivity and much reduced enantioselectivity. This study not only provides deeper insights into the functioning principles of SadPhos ligands but also offers valuable guidance for future ligand modifications and optimizations.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21933004), the Key-Area Research and Development Program of Guangdong Province (2020B010188001, 2020B0101350001), the Shenzhen Fundamental Research Program (GXWD20201231165807007-20200812124825001) and the Shenzhen Bay Laboratory Supercomputing Center.

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Authors and Affiliations

  1. State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Computational Chemistry and Drug Design, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055, China

    Bo Xiao & Yun-Dong Wu

  2. Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, China

    Tian-Yu Sun & Yun-Dong Wu

  3. Department of Chemistry, Fudan University, Shanghai, 200438, China

    Junliang Zhang

  4. College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Yun-Dong Wu

Authors
  1. Bo Xiao
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  4. Yun-Dong Wu
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Correspondence to Tian-Yu Sun, Junliang Zhang or Yun-Dong Wu.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without type-setting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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11426_2023_1701_MOESM1_ESM.docx

Theoretical Insight into the Activity and Selectivity in Palladium/Ming-Phos-Catalyzed Three-Component Asymmetric Synthesis of gem-Diarylmethine Silanes

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Xiao, B., Sun, TY., Zhang, J. et al. Theoretical insight into the activity and selectivity in palladium/Ming-Phos-catalyzed three-component asymmetric synthesis of gem-diarylmethine silanes. Sci. China Chem. 66, 2817–2827 (2023). https://doi.org/10.1007/s11426-023-1701-7

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  • DOI: https://doi.org/10.1007/s11426-023-1701-7

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