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Synthesis of a [2]Rotaxane Incorporating a “Magic Sulfur Ring” by the Thiol-Ene Click Reaction

Authors

  • Haiyan Zheng,

    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China)
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  • Prof. Yuliang Li,

    Corresponding author
    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    • CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
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  • Chunjie Zhou,

    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China)
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  • Dr. Yongjun Li,

    Corresponding author
    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    • CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
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  • Wenlong Yang,

    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China)
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  • Weidong Zhou,

    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China)
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  • Zicheng Zuo,

    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049 (P.R. China)
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  • Dr. Huibiao Liu

    1. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P.R. China), Fax: (+86) 10-82616576
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Abstract

The mild and highly efficient thiol-ene click reaction has been used to construct a rotaxane incorporating dibenzo-24-crown-8 (DB24C8) and a dibenzylammonium-derived thread in high yield under the irradiation of UV light. A rotaxane containing a disulfide linkage in the macrocycle was also synthesized by the thiol-ene click reaction. It has been demonstrated that the formation of the [2]rotaxane with the disulfide bond in the macrocycle occurs by a mechanism that is different to the threading-followed-by-stoppering process. The successful construction of a rotaxane directly from its constituent components, the macrocycle containing a disulfide linkage and the dibenzylammonium hexafluorophosphate salt, suggests that the space within the macrocycle incorporating the disulfide linkage is smaller than the phenyl unit and a plausible reaction mechanism has been proposed as follows: A small amount of the initiator forms two radicals upon the absorption of UV irradiation; the radicals act as a “key” to “unlock” the disulfide bond in the macrocycle. The resulting crown ether like moiety in the macrocycle is clipped around the ammonium ion center in the dumb-bell-shaped compound. The [2]rotaxane is generated upon recombination of the disulfide linkage.

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