有机化学 ›› 2021, Vol. 41 ›› Issue (2): 661-668.DOI: 10.6023/cjoc202010022 上一篇    下一篇

研究论文

铁催化酮羰基的硼化反应合成α-羟基硼酸酯

朱庆a,b, 夏春谷a, 刘超a,*()   

  1. a 中国科学院兰州化学物理研究所 兰州 730000
    b 中国科学院大学 北京 100049
  • 收稿日期:2020-10-16 修回日期:2020-10-30 发布日期:2020-11-04
  • 通讯作者: 刘超
  • 作者简介:
    * Corresponding author. E-mail:
  • 基金资助:
    国家自然科学基金(21673261); 国家自然科学基金(91745110); 国家自然科学基金(21872156); 江苏省自然科学基金(BK20190002); 江苏省自然科学基金(BK20181194); 中国科学院青年创新促进会(2018458)

Iron-Catalyzed Borylation of Ketones to α-Hydroxyboronates

Qing Zhua,b, Chungu Xiaa, Chao Liua,*()   

  1. a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
    b University of Chinese Academy of Sciences, Beijing 100049
  • Received:2020-10-16 Revised:2020-10-30 Published:2020-11-04
  • Contact: Chao Liu
  • Supported by:
    the National Natural Science Foundation of China(21673261); the National Natural Science Foundation of China(91745110); the National Natural Science Foundation of China(21872156); the Natural Science Foundation of Jiangsu Province(BK20190002); the Natural Science Foundation of Jiangsu Province(BK20181194); and the Youth Innovation Promotion Association CAS(2018458)

报道了一种铁催化烷基酮类化合物硼化合成三级α-羟基硼酸酯的反应, 使用了可商业购买的FeBr2作为催化剂, 加入醇作为添加剂来加速反应的进行, 同时避免副反应的发生. 通过该方法合成了一系列三级α-羟基硼酸酯化合物, 反应具有很好的底物兼容性以及官能团兼容性. 该铁催化剂对于大位阻的酮类化合物的硼化反应, 表现出优于铜催化的活性. 同时该反应可应用于克级规模的制备, 随后通过对三级α-羟基硼酸酯的C—O键进行官能化, 将所得的三级α-羟基硼酸酯转化为三级烷基硼酸酯以及偕二硼、偕硅硼类化合物.

关键词: 铁催化, α-羟基硼酸酯, 硼化反应,

Fe-catalyzed borylation of ketones to access tertiary α-hydroxyboronates has been demonstrated. In this transformation, commercially available FeBr2 was used as the catalyst, alcohols have been added to accelerate the transformation and avoid the side reaction. Various aliphatic ketones with different functional groups have been converted into tertiary α-hydroxyboronates. This transformation showed a particular tolerance for ketones with steric hinderance, which was distinguished from the traditional Cu catalyst. A gram scale reaction was also available. The alcoholic C—O functionalizations based onα-hydroxyboronates have been realized to access tertiary alkyl boronic esters, gem-diborylalkanes and gem- silylborylalkanes.

Key words: iron catalyst, α-hydroxyboronates, borylation, ketones