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Review
. 2022 Aug 8;13(37):10985-11008.
doi: 10.1039/d2sc01096h. eCollection 2022 Sep 28.

Fluorine in metal-catalyzed asymmetric transformations: the lightest halogen causing a massive effect

Samuel Lauzon  1 , Thierry Ollevier  1
Affiliations
Review

Fluorine in metal-catalyzed asymmetric transformations: the lightest halogen causing a massive effect

Samuel Lauzon et al. Chem Sci. .

Abstract

This review aims at providing an overview of the most significant applications of fluorine-containing ligands reported in the literature starting from 2001 until mid-2021. The ligands are classified according to the nature of the donor atoms involved. This review highlights both metal-ligand interactions and the structure-reactivity relationships resulting from the presence of the fluorine atom or fluorine-containing substituents on chiral catalysts.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Chiral fluorinated CPA ligands 1–4 in metal-catalyzed reactions.
Scheme 1
Scheme 1. [(Ra)-1]3/ScIII-catalyzed fluorination reaction.
Scheme 2
Scheme 2. (Sa)-4/InIII-catalyzed HDA and DA reactions.
Scheme 3
Scheme 3. Cyclopropanation reaction using chiral dirhodium catalysts.
Fig. 2
Fig. 2. TiIV– and MoVI–BINOLate complexes.
Scheme 4
Scheme 4. TiIV-Catalyzed sulfoxidation reaction – (R,R)-hydrobenzoin and (Ra)-BINOL derivatives.
Fig. 3
Fig. 3. TADDOL-like fluorous ligands.
Scheme 5
Scheme 5. Alkylation addition reaction of Ph2Zn to cinnamaldehyde – (Ra)-36vs. (Sa)-37.
Fig. 4
Fig. 4. Chiral RF–BINOL ligands for TiIV-catalyzed reactions in FBS.
Scheme 6
Scheme 6. Simultaneous ethylation reaction of aldehydes in FBS.
Scheme 7
Scheme 7. TiIV-Catalyzed ethylation reaction using α,α′-CnFn+1-diol ligands.
Scheme 8
Scheme 8. 2,2′-Bipyridine-α,α′-CF3-diol/ZnII-mediated ethylation reaction of aldehydes.
Scheme 9
Scheme 9. ZnII-Mediated ethylation reaction of 48 using Schiff's bases bearing an α-CF3-alcohol.
Scheme 10
Scheme 10. Et2Zn alkylation (left) and Reformatsky (right) reactions of benzaldehyde using amino-alcohol derivatives.
Scheme 11
Scheme 11. Postulated TS for the CuII-catalyzed aldol reaction.
Fig. 5
Fig. 5. Fluorinated bis(prolinol)phenol-type of ligands.
Scheme 12
Scheme 12. β-Amido chalcogen/PdII-catalyzed asymmetric allylic alkylation reaction.
Fig. 6
Fig. 6. Salen ligands bearing fluorinated motifs.
Scheme 13
Scheme 13. PhIO-assisted epoxidation reaction using chiral FeIII complexes.
Scheme 14
Scheme 14. Various applications of chiral RhII2 catalysts in diazo chemistry.
Scheme 15
Scheme 15. [2 + 1]-Cycloaddition reaction catalyzed by the [(R,R)-138]2/RhII2 complex.
Fig. 7
Fig. 7. Fluorinated motifs incorporated into DACH-type diimine ligands.
Scheme 16
Scheme 16. CuII-Catalyzed Diels–Alder reaction – diimine ligand screening.
Scheme 17
Scheme 17. CuI-Catalyzed carbene insertion reaction into the Si–H bond – chiral diimine possessing various bite angles.
Scheme 18
Scheme 18. Ni0-Catalyzed C-alkylation reaction – optimization of the chiral diamine ligand.
Scheme 19
Scheme 19. NiII complexes employed in addition-type reactions.
Fig. 8
Fig. 8. Perfluorinated motifs in chiral diamine- and diimine-based ligands.
Scheme 20
Scheme 20. Stereospecific preparation of C2-symmetric fluorinated DPEN ligands.
Scheme 21
Scheme 21. TiIV-Catalyzed epoxidation reaction of geraniol.
Fig. 9
Fig. 9. F-containing tosylated-(S,S)-DPEN ligands in RuII complexes.
Scheme 22
Scheme 22. RhIII-Catalyzed ATH reaction of 201 into (R)-202.
Scheme 23
Scheme 23. Friedel–Crafts alkylation reaction using chiral PHEBIM ligands.
Scheme 24
Scheme 24. CuI-Catalyzed allenylation reaction and the postulated TS.
Scheme 25
Scheme 25. MgII-Catalyzed dynamic kinetic asymmetric [3 + 2] cycloaddition reaction.
Fig. 10
Fig. 10. Fluorous chiral bis(oxazoline)-derived ligands.
Fig. 11
Fig. 11. Perfluoroalkyl motifs for chiral BOX ligands.
Scheme 26
Scheme 26. Ullman-like coupling reaction for the synthesis of PHOX ligands.
Scheme 27
Scheme 27. Postulated TS for the synthesis of isoflavone (R)-246.
Scheme 28
Scheme 28. (S)-247/Pd0-Catalyzed vinylborylation of alkenes.
Scheme 29
Scheme 29. PdII-Catalyzed allylic alkylation reaction using (S)-256 and (S)-257.
Scheme 30
Scheme 30. Asymmetric cyclopropanation reaction catalyzed by a CF3-containing PNNP/RuII complex.
Fig. 12
Fig. 12. Library of amine–phosphine ligands comprising the TF-BIPHAM scaffold.
Scheme 31
Scheme 31. Postulated TS for the attack of the azomethine ylide intermediate.
Scheme 32
Scheme 32. Two-step synthesis of 2-aminoalkyl furan via the alkynylation/cyclization reaction sequence.
Fig. 13
Fig. 13. Chiral ferrocenyl-derived ligands containing the 3,5-(CF3)2-C6H3 group.
Fig. 14
Fig. 14. Fluorinated JosiPhos- and WalPhos-type of ligands.
Scheme 33
Scheme 33. Hydrogenation reaction using electronically modified WalPhos ligands.
Scheme 34
Scheme 34. PdII-Catalyzed carbonylation reaction of styrene 20.
Fig. 15
Fig. 15. F-Containing MeO-BIPHEP derivatives.
Fig. 16
Fig. 16. Classes of axially chiral bisphosphine ligands comprising the 1,1′-biphenyl system.
Fig. 17
Fig. 17. Fluorous BINAPs employed in FBS.
Scheme 35
Scheme 35. (Ra,Sa)-330/RhI-Catalyzed hydroformylation reaction of alkenes.
Fig. 18
Fig. 18. Selected examples of chiral phosphoramidite ligands.
Fig. 19
Fig. 19. Miscellaneous mono- and bidentate P-ligands containing fluorine atoms.
Scheme 36
Scheme 36. (Ra)-349/PdII-catalyzed alkylation reaction of rac-114.
Scheme 37
Scheme 37. AuI-Catalyzed cyclization of 359 into (R)-360.
Scheme 38
Scheme 38. NHC–CuI-Catalyzed AAAr reaction of aliphatic allylic bromides with phenyl magnesium bromide.
Scheme 39
Scheme 39. Fluorination reaction via the optimized TS.
Fig. 20
Fig. 20. Chiral tfb-substituted ligands and their complexation modes with metals.
None
From left to right: Samuel Lauzon and Thierry Ollevier
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