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Steric-switched defluorofunctionalization selectivity: controlled synthesis of monofluoroalkene-masked medium-sized heterocyclic lactams and lactones

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Abstract

The steric-switched ipso-defluoroamination-triggered and ipso-defluorooxylation-triggered cyclization of (trifluoromethyl)alkenes with amino alcohols and diamines are achieved under mild conditions. This regioselective strategy distinguishes the different nucleophilic heteroatom sites in amino alcohols and unsymmetric diamines by the sequential defluorinative functionalization of two C(sp3)-F bonds in a CF3 group. Various attractive monofluoroalkene-masked medium-sized heterocyclic lactams and lactones are obtained in moderate to excellent yields. Simple derivation of these masked-heterocycles efficiently affords useful skeletons of lactams, lactones, and 1,4-oxazepanes in a single diastereoisomer. Mechanism studies indicate that a unique sequential ipso-/γ-selective defluorinative functionalization pathway is involved in these transformations.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21702064) and the Guangdong Basic and Applied Basic Research Foundation (2020B1515020012).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Key Lab of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou, 510640, China

    Hao Zeng, Hengyuan Li, Huanfeng Jiang & Chuanle Zhu

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  1. Hao Zeng
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  2. Hengyuan Li
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  3. Huanfeng Jiang
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  4. Chuanle Zhu
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Corresponding author

Correspondence to Chuanle Zhu.

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Conflict of interest

The authors declare no conflict of interest.

Supporting information

The supporting information is available online at http://chem.scichina.com and http://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.

Supporting Information

11426_2021_1135_MOESM1_ESM.pdf

Steric-Switched Defluorofunctionalization Selectivity: Controlled Synthesis of Monofluoroalkene-Masked Medium-Sized Heterocyclic Lactams and Lactones

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Zeng, H., Li, H., Jiang, H. et al. Steric-switched defluorofunctionalization selectivity: controlled synthesis of monofluoroalkene-masked medium-sized heterocyclic lactams and lactones. Sci. China Chem. 65, 554–562 (2022). https://doi.org/10.1007/s11426-021-1135-8

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  • DOI: https://doi.org/10.1007/s11426-021-1135-8

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