有机化学 ›› 2020, Vol. 40 ›› Issue (1): 53-60.DOI: 10.6023/cjoc201908017 上一篇    下一篇

研究论文

NN型双齿半夹心Ru(II)化合物:无受体脱氢环化合成喹啉和吡咯衍生物的催化剂

胡博文, 张宇哲, 尹鸽平, 陈大发   

  1. 哈尔滨工业大学化工与化学学院 哈尔滨 150001
  • 收稿日期:2019-08-11 修回日期:2019-09-16 出版日期:2020-01-25 发布日期:2019-09-25
  • 通讯作者: 胡博文 E-mail:bowenhu@hit.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.21672045,21871068)、中国博士后基金(No.2016M591519)、黑龙江省博士后基金(No.LBH-Z16069)及黑龙江省自然科学基金(Nos.B2018005,LC2018005)资助项目.

Half-Sandwich Ruthenium(II) Complexes with Bidentate NN Ligands:Active Catalysts for the Synthesis of Quinolines and Pyrroles by Acceptorless Dehydrogenative Cyclization

Hu Bowen, Zhang Yuzhe, Yin Geping, Chen Dafa   

  1. School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001
  • Received:2019-08-11 Revised:2019-09-16 Online:2020-01-25 Published:2019-09-25
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21672045, 21871068), the China Postdoctoral Science Foundation (No. 2016M591519), the Heilongjiang Provincial Postdoctoral Foundation (No. LBH-Z16069), and the National Natural Science Foundation of Heilongjiang Province (Nos. B2018005, LC2018005).

四个含NN型双齿配体的半夹心(h6-p-cymene)Ru(II)化合物被成功制备.这四个化合物分别为(h6-p-cymene)-Ru(C5H4N-C5H3N-OH)(1),(h6-p-cymene)Ru(C5H4N-CH2-C5H4N)(2),(h6-p-cymene)Ru(C5H4N-CH2-C5H3N-OH)(3)和(h6-p-cymene)Ru(C5H4N-CH2-C5H3N-OCH3)(4).这些化合物通过核磁氢谱、碳谱和元素分析等手段表征,化合物2的结构被X射线单晶衍射证实.将这些化合物应用于催化氨醇与酮的环化反应,其中3的催化效率最高.在0.5 mol%化合物3的存在下,制备了一系列喹啉和吡啶衍生物.

关键词: 半夹心, 钌, 无受体脱氢环化, 双齿配体, 2-羟基吡啶

Four (h6-p-cymene)Ru(II) complexes with bidentate NN ligands, (h6-p-cymene)Ru(C5H4N-C5H3N-OH) (1), (h6-p-cymene)Ru(C5H4N-CH2-C5H4N) (2), (h6-p-cymene)Ru(C5H4N-CH2-C5H3N-OH) (3) and (h6-p-cymene)Ru(C5H4N-CH2-C5H3N-OCH3) (4) were prepared. These complexes were all characterized by1H NMR, 13C NMR and elemental analysis, and complex 2 was further determined by single crystal crystallography. Complexes 1~4 were treated as catalysts for cyclizations of amino alcohols with ketones, and complex 3 exhibited the highest activity. The cyclization reactions proceeded in toluene with 0.5 mol% catalyst loading, and a series of quinolines and pyrroles were synthesized.

Key words: half-sandwich, ruthenium, acceptorless dehydrogenative cyclization, bidentate ligand, 2-hydroxypyridine