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Chiral rhodium(II)-catalyzed asymmetric aldol-type interception of an oxonium ylide to assemble chiral 2,3-dihydropyrans

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Abstract

A chiral dirhodium complex is an effective and robust catalyst for asymmetric carbene transformations. However, dirhodium-catalyzed asymmetric ylide interception processes are rare, mainly because of the dissociation of the metal catalyst before the stereo-determining step. Herein, we report a chiral dirhodium(II)-catalyzed asymmetric annulation of vinyl diazoesters with α-hydroxyl ketones, which provides an efficient way to form chiral 2,3-dihydropyrans in good yields with excellent diastereos-electivities and enantioselectivities. This article is the first example of the chiral dirhodium complex—controlled asymmetric aldol-type interception of an in situ—formed oxonium ylide. The origin of the high stereoselectivity is well expounded via experimental and computational studies. These generated chiral products exhibit potent antiproliferation activity in three tested cancer cell lines, namely HCT116 (colon cancer), A549 (lung adenocarcinoma), and SJSA-1 (osteosarcoma cancer).

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22001268, 21973113, 81973176), the Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery (2019B030301005), the Program for Guangdong Introducing Innovative and Entrepreneurial Teams (2016ZT06Y337) and the Guangdong Natural Science Fund (2020A1515010614), Key-Area Research and Development Program of Guangdong Province (2022B1111050003).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, 510006, China

    Aimin Xu, Rimei Zheng, Zhijing Zhang, Xinru Yin, Kemiao Hong, Yu Qian & Wenhao Hu

  2. School of Materials Science & Engineering, Sun Yat-sen University, Guangzhou, 510006, China

    Xiaoyu Zhou & Zhuofeng Ke

Authors
  1. Aimin Xu
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  2. Xiaoyu Zhou
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  3. Rimei Zheng
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  4. Zhijing Zhang
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  5. Xinru Yin
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  6. Kemiao Hong
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  7. Zhuofeng Ke
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  8. Yu Qian
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  9. Wenhao Hu
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Correspondence to Zhuofeng Ke, Yu Qian or Wenhao Hu.

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

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Chiral rhodium(II)-catalyzed asymmetric aldol-type interception of an oxonium ylide to assemble chiral 2,3-dihydropyrans

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Xu, A., Zhou, X., Zheng, R. et al. Chiral rhodium(II)-catalyzed asymmetric aldol-type interception of an oxonium ylide to assemble chiral 2,3-dihydropyrans. Sci. China Chem. 65, 1607–1614 (2022). https://doi.org/10.1007/s11426-022-1275-9

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  • DOI: https://doi.org/10.1007/s11426-022-1275-9

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