Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (8): 3134-3143.DOI: 10.6023/cjoc202103042 Previous Articles     Next Articles


Sc(OTf)3催化的δ-三氟甲基-δ-芳基-双取代对亚甲基苯醌和硫醇的反应: 高效合成二芳基甲烷硫醚化合物

李华a, 庞靖祥c, 刘华铮b, 赵长印b, 李松b, 王恒山a,*(), 刘希功b,*()   

  1. a 广西师范大学化学与药学学院 药用资源化学与药物分子工程国家重点实验室 广西民族医药协同创新中心 桂林 541004
    b 山东大学化学与化工学院 济南 250100
    c 山东第一医科大学药物研究所&山东省医学科学院 山东省医药生物技术中心 山东省罕见病重点实验室 国家卫生委员会生物技术药物重点实验室 济南 250000
  • 收稿日期:2021-03-23 修回日期:2021-04-19 发布日期:2021-05-25
  • 通讯作者: 王恒山, 刘希功
  • 作者简介:
    † 共同第一作者
  • 基金资助:
    国家自然科学基金(21801093); 国家自然科学基金(21977021); 国家自然科学基金(81760626); 中国博士后科学基金(2019M662321)

Sc(OTf)3-Catalyzed 1,6-Conjugate Addition of Thiols to δ-CF3-δ-aryl-disubstituted para-Quinone Methides: Efficient Construction of Diarylmethane Thioethers

Hua Lia, Jingxiang Pangc, Huazheng Liub, Changyin Zhaob, Song Lib, Hengshan Wanga(), Xigong Liub()   

  1. a State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004
    b School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100
    c Shandong Medicinal Biotechnology Centre, Key Laboratory for Rare & Uncommon Diseases of Shandong Province, Key Lab for Biotech-Drugs of National Health Commission, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 250000
  • Received:2021-03-23 Revised:2021-04-19 Published:2021-05-25
  • Contact: Hengshan Wang, Xigong Liu
  • About author:
    † (These authors contributed equally to this work).
  • Supported by:
    National Natural Science Foundation of China(21801093); National Natural Science Foundation of China(21977021); National Natural Science Foundation of China(81760626); China Postdoctoral Science Foundation(2019M662321)

An efficient and practical 1,6-conjuate addition reaction of δ-CF3-δ-aryl-disubstituted para-quinone methides with thiols has been described. This approach provides a straightforward access to structurally diverse diarylmethane thioethers bearing CF3-substituted quaternary stereocenters using 5 mol% Sc(OTf)3 as catalyst. The reaction has an excellent functional-group tolerance, and displays a broad scope with respect to both δ-CF3-δ-aryl-disubstituted para-quinone methides and thiophenols. Moreover, alkyl thioalcohols and benzylmercaptan have proven to be suitable substrates. Diarylmethane thioethers belong to an important structural scaffold that widely exists in a number of bioactive molecules and trifluoromethyl group has a profound effect on physiological properties of organic molecules. Therefore, the efficient method for the synthesis of diarylmethane thioethers bearing CF3-substituted quaternary stereocenters might provide a powerful strategy for the discovery of biologically interesting agents.

Key words: δ-CF3-δ-aryl-disubstituted, para-quinone methides, diarylmethane, thioethers, 1,6-conjuate addition