研究论文

含PNP配体铼配合物催化酮和醛转移加氢制醇性能研究

  • 段硕鹏 ,
  • 冯尚颂 ,
  • 李君笑 ,
  • 胡坤 ,
  • 李浩 ,
  • 方霄龙
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  • a安徽建筑大学 功能分子设计与界面过程重点实验室 合肥 230601;
    b安徽绿衡环保科技有限公司 芜湖 241007
†共同第一作者.

收稿日期: 2026-06-01

  修回日期: 2026-08-03

  网络出版日期: 2026-09-08

基金资助

国家自然科学基金(No. 21802010, 22401003)、安徽省自然科学基金(No. 2308085MB49)、安徽省教育厅优秀青年基金(No. 2023AH030038)、安徽建筑大学博士启动基金(No. 2023QDZ28)、安徽建筑大学质量工程(No. 2023jy71)资助项目.

Efficient Transfer Hydrogenation of Ketones and Aldehydes to Alcohols Catalysed by PNP-Rhenium Complexes

  • Duan Shuopeng ,
  • Feng Shangsong ,
  • Li Junxiao ,
  • Hu Kun ,
  • Li Hao ,
  • Fang Xiaolong
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  • aKey Laboratory of Functional Molecule Design and Interface Process, Anhui Jianzhu University, Hefei 230601;
    bAnhui Lvheng Environmental Protection Technology Co. Ltd., Wuhu 241007
†These authors contributed equally to this work.

Received date: 2026-06-01

  Revised date: 2026-08-03

  Online published: 2026-09-08

Supported by

Natural Science Foundation of China (No. 21802010, 22401003), the Natural Science Foundation of Anhui Province (No. 2308085MB49), the Fund for Outstanding Young Scholars of Anhui Province (No. 2023AH030038), the Scientific Research Startup Foundation of Anhui Jianzhu University (No. 2023QDZ28), and the Quality Engineering Foundation of Anhui Jianzhu University (No. 2023jy71).

摘要

将金属中心分别配位双齿PN配体、三齿PNP配体和四齿PNNP配体的Re(I)-NH配合物应用于催化酮和醛的转移加氢制醇反应. 研究发现, 膦胺配体的结构对所构成配合物的转移加氢性能有显著影响, 其中配合物HN(CH2CH2PPh2)2Re(CO)2Cl (7)活性最优. 在系统优化催化剂用量、助剂种类与用量、温度等参数的基础上, 活性测试结果表明, 7能有效催化近50种底物分子(包括芳香酮、脂肪酮、环酮以及芳香醛、脂肪醛)转移加氢制醇. 在合适反应条件下, 7还可以催化不饱和醛的选择性加氢, 高效制备不饱和醇.

本文引用格式

段硕鹏 , 冯尚颂 , 李君笑 , 胡坤 , 李浩 , 方霄龙 . 含PNP配体铼配合物催化酮和醛转移加氢制醇性能研究[J]. 有机化学, 2026 : 202604044 . DOI: 10.6023/cjoc202604044

Abstract

Rhenium(I)-NH complexes featuring bidentate PN, tridentate PNP, and tetradentate PNNP ligands were employed as catalysts for the transfer hydrogenation of ketones and aldehydes to alcohols. The structure of the phosphinoamine ligand significantly influenced the transfer hydrogenation performance of the resulting complexes, among which complex HN(CH2CH2PPh2)2Re(CO)2Cl (7) exhibited the highest activity. Following optimization of key factors including catalyst loading, additive, and temperature, activity tests demonstrated that 7 could efficiently catalyze the transfer hydrogenation of nearly 50 diverse ketones and aldehydes to their corresponding alcohols. Under suitable conditions, complex 7 also enabled the chemoselective hydrogenation of unsaturated aldehydes to afford unsaturated alcohols in high efficiency.

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