有机化学 ›› 2015, Vol. 35 ›› Issue (3): 618-624.DOI: 10.6023/cjoc201412049 上一篇    下一篇

研究论文

烯丙型醇与取代肼的对映专一性烯丙型烷基化反应

徐靖坤, 谷永红, 田仕凯   

  1. 中国科学技术大学化学系 合肥 230026
  • 收稿日期:2014-12-29 修回日期:2015-01-17 出版日期:2015-03-25 发布日期:2015-01-20
  • 通讯作者: 谷永红, 田仕凯 E-mail:ygu01@ustc.edu.cn;tiansk@ustc.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 21472178和21232007)、国家重点基础研究发展计划(No. 2014CB931800)和安徽省自然科学基金(No. 1408085MB24)资助项目.

Enantiospecific Allylic Alkylation of Substituted Hydrazines with Allylic Alcohols

Xu Jing-Kun, Gu Yonghong, Tian Shi-Kai   

  1. Department of Chemistry, University of Science and Technology of China, Hefei 230026
  • Received:2014-12-29 Revised:2015-01-17 Online:2015-03-25 Published:2015-01-20
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21472178 and 21232007), the National Key Basic Research Program of China (No. 2014CB931800), and the Natural Science Foundation of Anhui Province of China (No. 1408085MB24).

发展了首例烯丙型醇与取代肼的对映专一性烯丙型烷基化反应. 在钯/外消旋2,2'-双(二苯膦基)-1,1'-联萘(BINAP)/硼酸的催化下, 一系列高度对映富集的烯丙型醇与取代肼于室温进行烯丙型烷基化反应, 具有高度的区域选择性, 立体构型的保留率大于95%, 适于合成高对映纯度的烯丙型肼. 另外, 该反应的唯一副产物是水, 对环境友好.

关键词: 醇, 肼, 烯丙型烷基化, 钯, 对映专一性

Unprecedented enantiospecific allylic alkylation of substituted hydrazines with allylic alcohols has been developed. A range of substituted hydrazines underwent palladium/racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP)/boric acid-catalyzed allylic alkylation with highly enantioenriched allylic alcohols at room temperature and the reaction proceeded in a highly regioselective fashion with greater than 95% retention of configuration to afford allylic hydrazines with high enantiopurity. Moreover, only water was generated as an environmentally benign byproduct.

Key words: alcohols, hydrazines, allylic alkylation, palladium, enantiospecificity