Transition Metal⁃Catalyzed Cross⁃Coupling Reactions of Alkenyl Fluorides： Advances and Perspectives

doi:10.19894/j.issn.1000-0518.210235

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (5): 749-759.DOI: 10.19894/j.issn.1000-0518.210235

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Transition Metal⁃Catalyzed Cross⁃Coupling Reactions of Alkenyl Fluorides： Advances and Perspectives

Ya-Li FENG¹, Lie-Jin ZHOU²(), Zhong-Yan CAO³()

^1.School of Pharmacy and Chemical Engineering，Zhengzhou University of Industrial Technology，Zhengzhou 451100，China
^2.Key Laboratory of the Ministry of Education for Advanced Catalysis Materials，Department of Chemistry，Zhejiang Normal University，Jinhua 321004，China
^3.College of Chemistry and Chemical Engineering，Henan University，Kaifeng 475004，China

Received:2021-05-13 Accepted:2021-08-31 Published:2022-05-01 Online:2022-05-24
Contact: Lie-Jin ZHOU,Zhong-Yan CAO
About author:zycao@henu.edu.cn
ljzhou@zjnu.cn
Supported by:
the National Natural Science Foundation of China(21901233);the Key Scientific Research Projects of Colleges and Universities in Henan Province(21B350003)

Abstract

Abstract:

As one of the most important reactions for the construction of various of carbon carbon bonds and carbon heteroatom bonds， transition metal-catalyzed cross-coupling reactions of different organic （pseudo）halides with organometallic reagents have found wide applications. Reactive organic chlorides， bromides， iodides and （pseudo） halides are often employed as electrophiles in these transformations. Despite the strong bond dissociation energy of C—F bonds， there are many reports related to the transition metal-catalyzed cross-coupling reactions of aryl fluorides by activating their C—F bonds. Furthermore， recent studies have also disclosed that alkenyl fluorides can also be employed for a variety of cross-coupling reactions via similar activation strategy， which not only broadens the scope of cross-coupling reactions， but can also be applied for the facile synthesis of highly valued fine chemicals. In this review， insightful discussions on the latest achievements of the Pd or Ni-catalyzed cross-coupling reactions （Negishi， Suzuki-Miyaura， Kumada， Hiyama and Sonogashira） of mono- and polyfluoroniated alkenes are provided. The related mechanism considerations， limitations and the opportunities of the state-of-the-art methodologies will be highlighted， and the future development is prospected.

Key words: Alkenyl fluorides, C—F bond activation, Cross-coupling, Pd catalysis, Nickel catalysis

CLC Number:

O622.2

Ya-Li FENG, Lie-Jin ZHOU, Zhong-Yan CAO. Transition Metal⁃Catalyzed Cross⁃Coupling Reactions of Alkenyl Fluorides： Advances and Perspectives[J]. Chinese Journal of Applied Chemistry, 2022, 39(5): 749-759.

Figures/Tables 12

Fig.1 Pd（0）-catalyzed Negishi coupling reaction of 1，1-difluoroalkene with organozinc reagent［33］

Fig.2 Pd（0）-catalyzed Negishi coupling reaction of tetrafluoroethylene with zinc reagents［34］

Fig.3 Pd（0）-catalyzed Suzuki-Miyaura coupling reaction［35］

Fig.4 Pd（0）-catalyzed Suzuki-Miyaura coupling reaction of tetrasubstituted 1，1-difluoroalkenes［36］

Fig.5 Ni（0）-catalyzed Suzuki-Miyaura coupling reaction of 1，1-difluoroalkenes［37］

Fig.6 Nickel-catalyzed Kumada coupling reaction of 1，1-fluorohalo alkenes［38］

Fig.7 Kumada coupling reaction of 1，1-difluoroalkenes［39］

Fig.8 Kumada coupling reaction of di-Grignard reagents［40］

Fig.9 Kumada coupling reaction of fluorinated alkenes［39］

Fig.10 Kumada coupling reaction of monofluoroinated alkenes［41］

Fig.11 Pd（0）-catalyzed Hiyama coupling reaction of tetrafluoroethylene［42］

Fig.12 Pd（0）-catalyzed Sonogashira coupling reaction of tetrasubstituted 1，1-difluoroalkenes［43］

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Transition Metal⁃Catalyzed Cross⁃Coupling Reactions of Alkenyl Fluorides： Advances and Perspectives

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