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2020 , Vol. 40 >Issue 7: 2086 - 2093

DOI: https://doi.org/10.6023/cjoc202003058

研究论文

高效镁催化的羧酸硼氢化反应

  • 郑玉坤 ,
  • 曹旭 ,
  • 李佳 ,
  • 华海明 ,
  • 姚薇薇 ,
  • 赵斌林 ,
  • 马猛涛
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  • a 南京林业大学理学院 南京 210037;
    b 南京中医药大学药学院 南京 210023

收稿日期: 2020-03-25

  修回日期: 2020-04-26

  网络出版日期: 2020-05-11

基金资助

国家自然科学基金（Nos.21772093，21372117）和江苏省自然科学基金（No.BK20181421）资助项目.

收起

Efficient Magnesium-Catalyzed Hydroboration of Carboxylic Acids

  • Zheng Yukun ,
  • Cao Xu ,
  • Li Jia ,
  • Hua Haiming ,
  • Yao Weiwei ,
  • Zhao Binlin ,
  • Ma Mengtao
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  • a College of Science, Nanjing Forestry University, Nanjing 210037;
    b College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210023

Received date: 2020-03-25

  Revised date: 2020-04-26

  Online published: 2020-05-11

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21772093, 21372117) and the Natural Science Foundation of Jiangsu Province (No. BK20181421).

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摘要

在温和的反应条件下，较大空间位阻的氨基镁甲基化合物LMgCH3（THF）2[L=N（Ar）（SiMe3），Ar=4，2，6-Me（CHPh2）2C6H2]，可作为高效催化剂前体应用于一系列芳香族和脂肪族羧酸与频哪醇硼烷的脱氧硼氢化反应中.在同样反应条件下观察到羧酸对酯的化学选择性硼氢化.基于密度函数理论（DFT）计算和化学计量反应，提出了两种可能的羧酸硼氢化反应机理.

关键词： 硼氢化; 羧酸; 镁; 主族金属

本文引用格式

郑玉坤 , 曹旭 , 李佳 , 华海明 , 姚薇薇 , 赵斌林 , 马猛涛 . 高效镁催化的羧酸硼氢化反应[J]. 有机化学, 2020 , 40(7) : 2086 -2093 . DOI: 10.6023/cjoc202003058

Abstract

Sterically bulky amino magnesium methyl complex, LMgCH3(THF)2 (L=NAr(SiMe3), Ar=4,2,6-Me(CHPh2)2-C6H2) has been employed as an efficient precatalyst for the deoxygenate hydroboration of a variety of aromatic and aliphatic acids with pinacolborane (HBpin) under mild reaction condition. Additionally, chemoselective hydroboration of carboxylic acids over esters was also achieved under the standard conditions. Two plausible reaction mechanisms were proposed based on the density functional theory (DFT) calculations and stoichiometric reactions.

Key words： hydroboration; carboxylic acid; magnesium; main group metal

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