近日，天津大学化学学院教授Chun Zhang及Genping Huang研究组提出了铜催化含CF3基团的1,3-二烯的高选择性原硼化反应。2021年6月19日，国际知名学术期刊《德国应用化学》发表了这一成果。
据介绍，铜催化含CF3的共轭二烯与质子链和B2Pin2的高选择性原硼化反应已经被开发。这种化学反应可以抑制已知的脱氟反应，并提供含有完整的CF3基团的硼酸试剂。进一步研究表明，该化合物具有良好的官能团耐受性，产物可作为多种类型转化的前体。
该工作中，研究人员使用手性二膦配体，开发了首个使用这样的起始材料来合成带有CF3手性中心的烯丙基硼试剂的例子。值得注意的是，课题组通过DFT计算对反应机理进行了深入的研究，揭示了脱氟受到抑制的原因。
附：英文原文
Title: Copper-Catalyzed Highly Selective Protoboration of CF3-Containing 1,3-Dienes
Author: Chun Zhang, Juanjuan Wu, Hongli Wu, Xinzhi Li, Xinyu Liu, Qian Zhao, Genping Huang
Issue&Volume: 2021-06-19
Abstract: The copper-catalyzed highly selective protoboration of CF 3 -containing conjugated diene with proton source and B 2 pin 2 has been developed. This chemistry could suppress the well-known defluorination and provide borated reagents with an intact CF 3 -group. Further studies indicated that the functional group tolerance of this chemistry is very well, and the products could be used as versatile precursors for different types of transformations. Importantly, using chiral diphosphine ligand, we have developed the first example for using such starting material to synthesis allylic boron-reagents which bearing a CF 3 -containing chiral center. Notably, the reaction mechanism was intensively studied by DFT calculation, which could reveal the reason that defluorination was inhibited.
DOI: 10.1002/anie.202105896
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202105896
