Defluorinative Multi-Functionalization of Fluoroaryl Sulfoxides Enabled by Fluorine-Assisted Temporary Dearomatization
Mengjie Hu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023 China
These authors contributed equally to this work.
Search for more papers by this authorYuchen Liang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
These authors contributed equally to this work.
Search for more papers by this authorLiying Ru
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
These authors contributed equally to this work.
Search for more papers by this authorSheng Ye
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorLei Zhang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorXin Huang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorProf. Ming Bao
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023 China
Search for more papers by this authorLichun Kong
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorCorresponding Author
Prof. Bo Peng
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), Hunan Normal University, Changsha, 410081 China
Search for more papers by this authorMengjie Hu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023 China
These authors contributed equally to this work.
Search for more papers by this authorYuchen Liang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
These authors contributed equally to this work.
Search for more papers by this authorLiying Ru
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
These authors contributed equally to this work.
Search for more papers by this authorSheng Ye
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorLei Zhang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorXin Huang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorProf. Ming Bao
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023 China
Search for more papers by this authorLichun Kong
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Search for more papers by this authorCorresponding Author
Prof. Bo Peng
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004 China
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), Hunan Normal University, Changsha, 410081 China
Search for more papers by this authorGraphical Abstract
The potential reactivities of fluoroaryl sulfoxides have been unlocked by precisely constructing and elaborating their temporarily dearomatized intermediates via a robust [5,5]-sulfonium-rearrangement-triggered dearomatization/rearomatization process. Impressively, fluorine has shown its irreplaceable role for the success of the reaction.
Abstract
Owing to its unique physical properties, fluorine is often used to open up new reaction channels. In this report, we establish a cooperation of [5,5]-rearrangement and fluorine-assisted temporary dearomatization for arene multi-functionalization. Specifically, the [5,5]-rearrangement of fluoroaryl sulfoxides with β,γ-unsaturated nitriles generates an intriguing dearomatized sulfonium species which is short-lived but exhibits unusually high electrophilicity and thus can be instantly trapped by nucleophiles and dienes at a remarkably low temperature (−95 °C) to produce four types of valuable multi-functionalized benzenes, respectively, involving appealing processes of defluorination, desulfurization, and sulfur shift. Mechanistic studies indicate that the use of fluorine on arenes not only circumvents the generally inevitable [3,3]-rearrangement but also impedes the undesired rearomatization process, thus provides a precious space for constructing and elaborating the temporarily dearomatized fluorinated sulfonium species.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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