有机化学 ›› 2017, Vol. 37 ›› Issue (12): 3170-3176.DOI: 10.6023/cjoc201708001 上一篇    下一篇

研究论文

半三明治型铱催化剂催化氢化葡萄糖制备山梨糖醇

龚宝祥, 严龙, 陈蒙远, 邓晋, 傅尧   

  1. 中国科学技术大学化学与材料科学学院 安徽省生物质洁净能源重点实验室 230026
  • 收稿日期:2017-08-01 修回日期:2017-08-31 发布日期:2017-09-15
  • 通讯作者: 邓晋, 傅尧 E-mail:dengjin@ustc.edu.cn;fuyao@ustc.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21572212,21402181,21325208)、中国科学院项目基金(Nos.XDB20000000,YZ201563)、中央高校基础研究经费、教育部长江学者和创新团队发展计划、安徽省科技攻关计划(No.1604a0702027)资助项目.

Preparation of D-Sorbitol by Catalytic Hydrogenation of D-Glucose with Semi Sandwich Iridium Catalyst

Gong Baoxiang, Yan Long, Chen Mengyuan, Deng Jin, Fu Yao   

  1. Anhui Province Key Laboratory of Biomass Clean Energy, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026
  • Received:2017-08-01 Revised:2017-08-31 Published:2017-09-15
  • Contact: 10.6023/cjoc201708001 E-mail:dengjin@ustc.edu.cn;fuyao@ustc.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21572212, 21402181, 21325208), the Science Foundation of the Chinese Academy of Sciences (Nos. XDB20000000, YZ201563), the Fundamental Research Funds for the Central Universities, the Program for Changjiang Scholars and Innovative Research Team in University of the Ministry of Education of China, the Key Technologies R&D Programme of Anhui Province (No. 1604a0702027).

使用[Cp*Ir-(di-OH-bpy)(OH2)][SO4](di-OH-bpy=4,4'-二羟基-2,2'-联吡啶)作催化剂,高效实现了葡萄糖开环加氢制备山梨糖醇.通过氢源的比较和氢气作为氢源的条件优化,山梨糖醇最高产率可达96%.同时研究了铱催化剂中不同配体对加氢效果的影响,并对氢化过程可能的机理进行了相应阐述.Cp*Ir与氢气的催化体系具有反应条件温和、产物选择性高等优点,为其他生物质基平台分子的催化加氢制备高附加值化学品提供了一种有效的方法.

关键词: 葡萄糖, 山梨糖醇, 铱催化剂, 均相加氢, 联吡啶配体

[Cp*Ir-(di-OH-bpy)(OH2)] [SO4] (di-OH-bpy=4,4'-dihydroxyl-2,2'-bipyridine) exhibited high catalytic performance during the hydrogenation of D-glucose to D-sorbitol. Using formic acid as hydrogen source led to an unsatisfactory D-sorbitol selectivity. The ring-opening hydrogenation of glucose was efficiently achieved by hydrogen. Under optimal conditions, D-sorbitol could be obtained in 96% yield. The effect of different ligands in iridium catalyst on hydrogenation was also investigated. A speculated mechanism was proposed to illustrate the detailed process of D-glucose hydrogenation to produce sorbitol. The catalytic system has the merits of relatively mild reaction conditions and high product selectivity, which provides an effective method for the catalytic hydrogenation of other biomass-based platform chemicals.

Key words: glucose, sorbitol, Cp*Ir, homogeneous hydrogenation, bipyridine ligand