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Palladium-catalyzed hydrosilylation of ynones to access silicon-stereogenic silylenones by stereospecific aromatic interaction-assisted Si-H activation

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Abstract

Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes. However, the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult. Here we report a highly enantioselective hydrosilylation of ynones, a type of carbonyl-activated alkynes, using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand. The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94% yield, >20:1 regioselectivity and 98:2 enantioselectivity. The density functional theory (DFT) calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity, in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C-H-π interaction and aromatic cavity-oriented enantioselectivity-determining step during desymmetric functionalization of Si-H bond.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21773051, 22072035, 21703051, 21801056, 21901056), Zhejiang Provincial Natural Science Foundation of China (LZ18B020001, LY18B020013, LQ19B040001). The authors thank L. Li, K.Z. Jiang and X.Q. Xiao for their assistance on the MS and X-ray analysis.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou, 311121, China

    Jia-Le Xie, Zheng Xu, Han-Qi Zhou, Yi-Xue Nie, Jian Cao, Guan-Wu Yin & Li-Wen Xu

  2. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute (SRI), Lanzhou Institute of Chemical Physics (LICP), University of the Chinese Academy of Sciences (UCAS), Lanzhou, 730000, China

    Li-Wen Xu

  3. Normandie University, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), Rouen, 76000, France

    Jean-Philippe Bouillon

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  1. Jia-Le Xie
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  2. Zheng Xu
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  3. Han-Qi Zhou
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  4. Yi-Xue Nie
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  7. Jean-Philippe Bouillon
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Correspondence to Li-Wen Xu.

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11426_2020_9939_MOESM1_ESM.pdf

Palladium-Catalyzed Hydrosilylation of Ynones to Access Silicon-Stereogenic Silylenones by Stereospecific Aromatic Interaction-assisted Si-H Activation

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Xie, JL., Xu, Z., Zhou, HQ. et al. Palladium-catalyzed hydrosilylation of ynones to access silicon-stereogenic silylenones by stereospecific aromatic interaction-assisted Si-H activation. Sci. China Chem. 64, 761–769 (2021). https://doi.org/10.1007/s11426-020-9939-1

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  • DOI: https://doi.org/10.1007/s11426-020-9939-1

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