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Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer

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Listed:
  • Zhaoliang Yang

    (Wuhan University)

  • Yunhong Niu

    (Wuhan University)

  • Xiaoqian He

    (Chongqing University)

  • Suo Chen

    (Wuhan University)

  • Shanshan Liu

    (Wuhan University)

  • Zhengyu Li

    (Wuhan University)

  • Xiang Chen

    (Wuhan University)

  • Yunxiao Zhang

    (Wuhan University)

  • Yu Lan

    (Chongqing University
    Zhengzhou University)

  • Xiao Shen

    (Wuhan University)

Abstract

Controlling the reactivity of reactive intermediates is essential to achieve selective transformations. Due to the facile 1,5-hydrogen atom transfer (HAT), alkoxyl radicals have been proven to be important synthetic intermediates for the δ-functionalization of alcohols. Herein, we disclose a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals. The efficient radical 1,2-silyl transfer (SiT) allows us to make various α-functionalized products from alcohol substrates. Compared with the direct generation of α-carbon radicals from oxidation of α-C-H bond of alcohols, the 1,2-SiT strategy distinguishes itself by the generation of alkoxyl radicals, the tolerance of many functional groups, such as intramolecular hydroxyl groups and C-H bonds next to oxygen atoms, and the use of silyl alcohols as limiting reagents.

Suggested Citation

  • Zhaoliang Yang & Yunhong Niu & Xiaoqian He & Suo Chen & Shanshan Liu & Zhengyu Li & Xiang Chen & Yunxiao Zhang & Yu Lan & Xiao Shen, 2021. "Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:12:y:2021:i:1:d:10.1038_s41467-021-22382-y
    DOI: 10.1038/s41467-021-22382-y
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    Cited by:

    1. Yunxiao Zhang & Yizhi Zhang & Chen Ye & Xiaotian Qi & Li-Zhu Wu & Xiao Shen, 2022. "Cascade cyclization of alkene-tethered acylsilanes and allylic sulfones enabled by unproductive energy transfer photocatalysis," Nature Communications, Nature, vol. 13(1), pages 1-11, December.

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