Fluorination Triggers Fluoroalkylation: Nucleophilic Perfluoro-tert-butylation with 1,1-Dibromo-2,2-bis(trifluoromethyl)ethylene (DBBF) and CsF
Dr. Qian Wang
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
Search for more papers by this authorQuan Tao
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
CAS Center for ExcelleNce in Superconducting Electronics (CENSE), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences (UCAS), Beijing, 100049 China
Search for more papers by this authorDr. Hui Dong
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
CAS Center for ExcelleNce in Superconducting Electronics (CENSE), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences (UCAS), Beijing, 100049 China
Search for more papers by this authorDr. Chuanfa Ni
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
Search for more papers by this authorCorresponding Author
Prof. Xiaoming Xie
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
CAS Center for ExcelleNce in Superconducting Electronics (CENSE), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences (UCAS), Beijing, 100049 China
Search for more papers by this authorCorresponding Author
Prof. Jinbo Hu
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
Search for more papers by this authorDr. Qian Wang
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
Search for more papers by this authorQuan Tao
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
CAS Center for ExcelleNce in Superconducting Electronics (CENSE), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences (UCAS), Beijing, 100049 China
Search for more papers by this authorDr. Hui Dong
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
CAS Center for ExcelleNce in Superconducting Electronics (CENSE), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences (UCAS), Beijing, 100049 China
Search for more papers by this authorDr. Chuanfa Ni
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
Search for more papers by this authorCorresponding Author
Prof. Xiaoming Xie
State Key Laboratory of Functional Materials of Informatics, Shanghai Institute of Microsystem and Information Technology (SIMIT), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
CAS Center for ExcelleNce in Superconducting Electronics (CENSE), Chinese Academy of Sciences (CAS), Shanghai, 200050 China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences (UCAS), Beijing, 100049 China
Search for more papers by this authorCorresponding Author
Prof. Jinbo Hu
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
Search for more papers by this authorGraphical Abstract
A new perfluoro-tert-butylation protocol debuts: Consecutive triple fluorinations of 1,1-dibromo-2,2-bis(trifluoromethyl)ethylene (DBBF) generate (CF3)3C− species, which enables efficient nucleophilic perfluoro-tert-butylation of various electrophiles. The C(CF3)3-containing products can be successfully applied in 19F-magnetic resonance imaging.
Abstract
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 (CF3)3C− 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 1H- and 19F-magnetic resonance imaging (MRI) experiment with an ultra-low field (ULF) MRI system.
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