有机化学 ›› 2017, Vol. 37 ›› Issue (8): 2066-2072.DOI: 10.6023/cjoc201701032 上一篇    下一篇

研究论文

草酰胺导向下钯催化的C(sp2)—H和C(sp3)—H键的直接酰氧基化反应

郑永祥, 韩健, 黄志斌, 史达清, 赵应声   

  1. 苏州大学材料与化学化工学部 苏州 215123
  • 收稿日期:2017-01-16 修回日期:2017-03-22 出版日期:2017-08-25 发布日期:2017-04-13
  • 通讯作者: 史达清, 赵应声 E-mail:dqshi@suda.edu.cn;yszhao@suda.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21403148,21572149)和江苏省高校自然科学重大研究(No.15KJA150006)资助项目.

Palladium-Catalyzed Direct Acyloxylation of C (sp2)—H and C (sp3)—H Bonds under the Assistance of Oxalyl Amide

Zheng Yongxiang, Han Jian, Huang Zhibin, Shi Daqing, Zhao Yingsheng   

  1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123
  • Received:2017-01-16 Revised:2017-03-22 Online:2017-08-25 Published:2017-04-13
  • Contact: 10.6023/cjoc201701032 E-mail:dqshi@suda.edu.cn;yszhao@suda.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21403148, 21572149) and the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 15KJA150006).

成功地发展了一种草酰胺导向的钯催化的过氧化苯甲酸叔丁酯为氧化剂的C(sp2)—H和C(sp3)—H键的酰氧基化反应.草酰胺基保护的苄胺用过氧化苯甲酸叔丁酯或羧酸为酰氧基化剂可以选择性地进行C(sp2)—H键的酰氧基化,而草酰氨基保护的2-烷基苯胺则可以进行苄基位C(sp3)—H键的酰氧基化反应.该方法为芳香酸酯类化合物的合成提供了一种方便、有效的方法.

关键词: 酰氧基化反应, C(sp3)—H键, C(sp2)—H键

A practical palladium-catalyzed direct acyloxylation of C(sp2)—H and C(sp3)—H bonds under the assistance of oxalyl amide with TBPB as oxidant was developed. Selective acyloxylation of C(sp2)—H bond for oxalyl amide protected benzyl amine using TBPB or carboxylic acids as acyloxylating reagent was achieved. For oxalyl amide protected 2-alkylanilines, the selective acyloxylation of benzylic C(sp3)—H bond was also achieved. This protocol provided an efficient and practical method for the synthesis of aryl esters.

Key words: acyloxylation, C(sp2)—H bond, C(sp3)—H bond