Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China.
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050, China.
Angew Chem Int Ed Engl. 2021 Dec 20;60(52):27318-27323. doi: 10.1002/anie.202113727. Epub 2021 Nov 18.
Perfluoro-tert-butylation reaction has long remained a challenging task. We now report the use of 1,1-dibromo-2,2-bis(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 ) 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 was successfully applied in H- and F-magnetic resonance imaging (MRI) experiment with an ultra-low field (ULF) MRI system.
全氟叔丁基化反应一直是一项具有挑战性的任务。我们现在首次报道了 1,1-二溴-2,2-双（三氟甲基）乙烯（DBBF）作为全氟叔丁基化反应的实用试剂。通过与 DBBF 和 CsF 的连续三氟化过程，可以释放和观察（CF ） C 物种，它可以作为各种亲电试剂的强亲核全氟叔丁基化试剂。该合成方案的强大功能体现在高效合成结构多样的全氟叔丁基化分子上。多种应用证明了该方法的实用性，以及全氟叔丁基化合物作为灵敏探针的优越性。全氟叔丁基化产物成功地应用于超低场 (ULF) MRI 系统的 H-和 F-磁共振成像 (MRI) 实验中。
