Recent Progress in Selective C-F Bond Activation of Trifluoromethyl Alkenes

doi:10.6023/cjoc202210016

Abstract

Selective C-F bond activation of the trifluoromethyl group is an important approach for the synthesis of gem-difluoro compounds. Given the importance of trifluoromethyl alkenes in synthetic chemistry as well as their diversity in selectivity, the research on selective C-F bond activation of these compounds has received considerable interest. To this end, The research progress is summarized, including nucleophilic addition/defluorination (S_N2' type), acid-promoted defluorinative Friedel-Crafts arylation, (formal) ipso-defluorinative functionalization, and transition-metal-catalyzed migratory insertion/ defluorination.

Key words: trifluoromethyl alkene, C-F bond activation, synthetic method

Cite this article

Shuyong Song, Senmiao Xu. Recent Progress in Selective C-F Bond Activation of Trifluoromethyl Alkenes[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 411-425.

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Fig. & Tab. 28

Scheme 1. Selective C-F activation of trifluoromethyl alkenes

Scheme 2. SN2'-type substitution reactions involving different nucleophiles

Scheme 3. Super base-Mediated gem-difluoroalkenylations of sulfoximines

Scheme 4. Decarboxylative/defluorinative alkylation for the synthesis of gem-difluoroalkenes

Scheme 5. Sequential substitution of fluorine atoms for the synthesis of 3-fluoropyrazoles

Scheme 6. Sequential substitution of fluorine atoms for the synthesis of fluorinated 4H-pyran

Scheme 7. Lewis acid promoted single C-F activation in 1-CF3-alkenes

Scheme 8. ipso-Defluorooxylation of (trifluoromethyl)alkenes with oximes

Scheme 9. ipso-Defluorinative amination triggered 1,3-diamination of (trifluoromethyl)alkenes

Scheme 10. Defluoroalkylation of C-F bonds of industrially relevant hydrofluoroolefins

Scheme 11. Selective single C-F bond arylation of trifluoromethyl alkene derivatives

Scheme 12. Selective C-F bond allylation of trifluoromethyl alkenes

Scheme 13. Copper-catalyzed carboxylation of C-F Bonds with CO2

Scheme 14. Pd-catalyzed 5-endo cyclization through β-fluorine elimination using oxime derivatives

Scheme 15. Rh-catalyzed arylation of an allylic C-F bond of trifluoromethyl alkenes

Scheme 16. Ni-mediated/catalyzed allylic C(sp3)-F bond activation of trifluoromethyl groups

Scheme 17. Migratory functionalization of unactivated alkyl bromides for construction of all-carbon quaternary centers

Scheme 18. Ni-catalyzed radical-promoted defluoroalkylborylation of trifluoromethyl alkenes

Scheme 19. Copper-catalyzed alkylation of an allylic C-F bond of trifluoromethyl alkene

Scheme 20. Copper-catalyzed alkylation of an allylic C-F bond of trifluoromethyl alkenes

Scheme 21. Cu- or Fe-catalyzed borylation of an allylic C-F bond of 2-trifluoromethyl-1-alkenes

Scheme 22. Copper(I)-catalyzed boryl substitution of 1-trifluoromethyl allenes

Scheme 23. Copper-catalyzed asymmetric defluoroborylation of 1-(trifluoromethyl)alkenes

Scheme 24. Copper(I)-catalyzed enantioselective γ-boryl substitution of trifluoromethyl-substituted alkenes

Scheme 25. Cu-catalyzed enantioselective defluoroborylation and defluorosilylation of 1-(trifluoromethyl)alkenes

Scheme 26. Cu(II)-catalyzed enantioselective diborylation of 1-chloro-1-trifluoromethylalkenes

Scheme 27. Copper-catalyzed asymmetric enantioselective defluorosilylation of trifluoromethylated alkenes

Scheme 28. Cu(I)-catalyzed enantioselective γ-boryl substitution of trifluoromethyl- and silyl-substituted alkenes

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