中科院上海有机化学研究所胡金波团队报道了氟化引发氟烷基化：DBBF和CsF的亲核全氟叔丁基化。相关研究成果于2021年10月29日发表在国际顶尖学术期刊《德国应用化学》。

全氟叔丁基化反应一直是一项具有挑战性的任务。

该文中，研究人员首次报道使用1,1-二溴-2,2bis（三氟甲基）乙烯（DBBF）作为全氟-叔丁基化反应的实用试剂。通过DBBF和CsF的连续三重氟化过程，(CF3)3C物种可以被释放和观察到，能够作为各种亲核全氟叔丁基试剂。该合成方法的威力通过结构多样的全氟叔丁基化分子的高效合成得到证明。

多个应用证明了该方法的实用性，以及全氟叔丁基化合物作为敏感探针的优越性。全氟叔丁基化产物3t已成功应用于超低场（ULF）MRI系统的¹H和¹⁹F磁共振成像（MRI）实验。

附：英文原文

Title: Fluorination Triggers Fluoroalkylation: Nucleophilic Perfluoro-tert-butylation with DBBF and CsF

Author: Qian Wang, Quan Tao, Hui Dong, Chuanfa Ni, Xiaoming Xie, Jinbo Hu

Issue&Volume: 2021-10-29

Abstract: Perfluoro-  tert  -butylation reaction has long remained a challenging task. We now report the use of 1,1-dibromo-2,2bis(trifluoromethyl)ethylene (DBBF) as a practical reagent for perfluoro-  tert  -butylation reactions for the first time. Through a consecutive triple-fluorination process with DBBF and CsF, the (CF  3  )  3  C    species can be liberated and observed, which is able to serve as a robust nucleophilic perfluoro-  tert  -butylating agent for various electrophiles. The power of this synthetic protocol is evidenced by the efficient synthesis of structurally diverse perfluoro  tert  -butylated molecules. Multiple applications demonstrate the practicability of this method, as well as the superiority of perfluoro  tert  -butylated compounds as sensitive probes. The perfluoro-  tert  butylated product  3t  was successfully applied in  1  H- and  19  Fmagnetic resonance imaging (MRI) experiment with an ultra-low field (ULF) MRI system.

DOI: 10.1002/anie.202113727

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202113727