有机化学 ›› 2020, Vol. 40 ›› Issue (11): 3925-3933.DOI: 10.6023/cjoc202004025 上一篇    下一篇

研究论文

钯(II)催化共轭二烯的需氧氧化1,2-双乙酰氧基化反应

居辰阳, 吴正兴, 李云艺, 张万斌   

  1. 上海交通大学化学化工学院 变革性分子前沿科学中心 上海市手性药物分子工程重点实验室 上海 200240
  • 收稿日期:2020-04-16 修回日期:2020-05-19 发布日期:2020-05-29
  • 通讯作者: 吴正兴, 张万斌 E-mail:wzxtheway@sjtu.edu.cn;wanbin@sjtu.edu.cn
  • 基金资助:
    上海市教育委员会(No.201701070002E00030)、上海市青年科技英才扬帆计划(No.19YF1421900)、上海市科学技术委员会(No.19JC1430100)和国家自然科学基金(Nos.21620102003,21831005,21901158,21991112)资助项目.

Palladium(II)-Catalyzed Aerobic 1,2-Diacetoxylation of Conjugated Dienes

Ju Chenyang, Wu Zhengxing, Li Yunyi, Zhang Wanbin   

  1. Shanghai Key Laboratory for Molecular Engineering and Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiaotong University, Shanghai, 200240
  • Received:2020-04-16 Revised:2020-05-19 Published:2020-05-29
  • Supported by:
    Project supported by the Shanghai Municipal Education Commission (No. 201701070002E00030), the Shanghai Sailing Program (No. 19YF1421900), the Science and Technology Commission of Shanghai Municipality (No. 19JC1430100), and the National Natural Science Foundation of China (Nos. 21620102003, 21831005, 21901158, 21991112).

邻二醇类化合物在农药、手性医药以及精细化学品等方面具有重要的用途.发展了一种钯(II)催化共轭二烯的1,2-双乙酰氧基化的方法,利用简单易得的醋酸作为氧源,氧气作为氧化剂,高区域选择性地实现了共轭二烯的1,2-双乙酰氧基化反应.本方法对芳基、酯基和羰基等取代的共轭二烯具有良好的底物适应性,催化产物经过简单醇解或水解转化为邻二醇化合物,是一种高效合成邻二醇类化合物的新策略.

关键词: 钯, 共轭二烯, 1,2-双乙酰氧基化, 邻二醇

1,2-Diols have important applications in pesticides, chiral medicines and fine chemicals. A Pd(II)-catalyzed 1,2-diacetoxylation method using readily available acetic acid as the oxygen source and oxygen as the oxidant was developed. For the 1,2-diacetoxylation of conjugated dienes, the reaction proceeds with high 1,2-regioselectivity. This protocol has good substrate scope for conjugated dienes possessing aryl-, ester-and carbonyl groups. The catalytic products can be transformed to 1,2-diols through simple alcoholysis or hydrolysis, therefore it is an efficient method for the synthesis of 1,2-diols.

Key words: palladium, conjugated diene, 1,2-diacetoxylation, 1,2-diol