Recent Advances in the Construction of Fluorinated Organoboron Compounds

Abstract

Fluorinated organoboron compounds are important synthetic building blocks that combine the unique characteristics of a fluorinated motif with the versatile synthetic applications of organoboron moiety. This review article guides the research on fluorinated organoboron compounds mainly from four aspects in recent years: selective monodefluoroborylation of polyfluoroarenes and polyfluoroalkenes, selective borylation of fluorinated substrates, selective fluorination of organoboron compounds, and borofluorination of alkynes/olefins. In addition, this review will provide a necessary guidance and inspiration for the research on the valuable synthetic building block fluorinated organoboron compounds.

Scheme 1. (A) Selected Fluorine-Containing Drug Molecules and Materials Science, (B) Selected Valuable Boron-Containing Molecules and Their Versatile Synthetic Applications and (C) Selected Valuable Fluorinated Boron-Containing Molecules

Scheme 2. Rh-Catalyzed Monodefluoroborylation of Polyfluoroarenes

Scheme 3. Ni-Catalyzed Selective Monodefluoroborylation of Polyfluoroarenes

Scheme 4. Selective Monodefluoroborylation of gem-Difluoroalkenes (Top), Copper-Catalyzed Regioselective Monodefluoroborylation of Polyfluoroalkenes En Route to Diverse Fluoroalkenes (Middle), and Proposed Mechanism (Bottom)

Scheme 5. Selective Asymmetric Monodefluoroborylation of β-Trifluoromethyl and Difluoromethyl Alkenes as Well as Rhodium-Catalyzed Formation of 2-Fluoroalkyl-1,3,2-dioxaborolanes by Catalytic Functionalization of Hexafluoropropene

Scheme 6. C–F Activation at Rhodium–Boryl Complexes

Scheme 7. Radical-Promoted Selective Monodefluoroborylation of Polyfluoroarenes

Scheme 8. Regioselective Hydroboration of Fluoroolefins

Scheme 9. Copper-Catalyzed Borylation of CF₃-Containing 1,3-Enynes

Scheme 10. ortho-C–H Borylation of Arenes with Fluorine-Containing Compounds as Directing Groups

Scheme 11. Reactions of 2,2,2-Trifluorodiazoethane with Organoboron Compounds and Proposed Mechanism

Scheme 12. (i) Dechlorination–Carboboration of gem-Dichloroalkanes and (ii) Ring-Opening Lithiation–Borylation of 2-Trifluoromethyl Oxirane

Scheme 13. (a,b) Regioselective Radical Hydroboration of gem-Difluoroalkenes and (c) Regioselective Radical Hydroboration of Trifluoromethylalkenes

Scheme 14. (a–c) Borylations of Fluorinated Alkenyl/Aryl Metal Reagents, (d) Nucleophilic Fluoroalkylation of Bromomethyl Boronates with Silicon Reagents, (e) Homologation of Alkyl Boronic Esters, (f) Homolytic Substitution of Haloarenes, and (g) Selective Dual C–H/C–B Borylation of Haloarenes

Scheme 15. Selective α-Fluorination and Trifluoromethylation of Alkenyl MIDA Boronates and Proposed Mechanism

Scheme 16. gem-Difluorination of Alkenyl MIDA Boronates and Reaction Mechanism and an Iodofluorination of Alkynyl or Alkenyl MIDA Boronates

Scheme 17. Fluorinations/Perfluoroalkylations of Boronate Complexes

Scheme 18. Palladium-Catalyzed Difluoroalkylation–Borylation of Alkynes and Proposed Mechanism

Scheme 19. (i) Copper-Catalyzed Borofluorination of Alkynes and (ii) Dual-Catalysis-Promoted Boryldifluoroallylation of Alkynes

Scheme 20. (I) Copper-Catalyzed Borylfluoromethylation of Alkenes and (II) Light-Induced Borofluoroalkylation of Unactivated Alkenes and Proposed Mechanism

Scheme 21. (i) Integrated Redox-Active Reagents for Photoinduced Regio- and Stereoselective Fluorocarboborylation, (ii,iii) Perfluoroalkyl Radical-Induced 1,2,3-Trifunctionalization of Allylboronates, (iv) Fluorinated 1,n-Bisborylalkanes via Remote Radical Boron Migration, and (v) Photoinduced Weak Base-Catalyzed Synthesis of α-Haloboronates from Vinylboronates and Polyfluoroalkyl Halides