Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation
- Grégory Landelle,
- Armen Panossian,
- Sergiy Pazenok,
- Jean-Pierre Vors and
- Frédéric R. Leroux
Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287
Graphical Abstract
Scheme 1: Pd-catalyzed monofluoromethylation of pinacol phenylboronate [44].
Scheme 2: Cu-catalyzed monofluoromethylation with 2-PySO2CHFCOR followed by desulfonylation [49].
Scheme 3: Cu-catalyzed difluoromethylation with α-silyldifluoroacetates [57].
Figure 1: Mechanism of the Cu-catalyzed C–CHF2 bond formation of α,β-unsaturated carboxylic acids through dec...
Scheme 4: Fe-catalyzed decarboxylative difluoromethylation of cinnamic acids [62].
Scheme 5: Preliminary experiments for investigation of the mechanism of the C–H trifluoromethylation of N-ary...
Figure 2: Plausible catalytic cycle proposed by Z.-J. Shi et al. for the trifluoromethylation of acetanilides ...
Figure 3: Plausible catalytic cycle proposed by M. S. Sanford et al. for the perfluoroalkylation of simple ar...
Figure 4: Postulated reaction pathway for the Ag/Cu-catalyzed trifluoromethylation of aryl iodides by Z. Q. W...
Figure 5: Postulated reaction mechanism for Cu-catalyzed trifluoromethylation reaction using MTFA as trifluor...
Scheme 6: Formal Heck-type trifluoromethylation of vinyl(het)arenes by M. Sodeoka et al. [83].
Figure 6: Proposed catalytic cycle for the copper-catalyzed trifluoromethylation of (het)arenes in presence o...
Figure 7: Proposed catalytic cycle for the copper-catalyzed trifluoromethylation of N,N-disubstituted (hetero...
Figure 8: Proposed catalytic cycle by Y. Zhang and J. Wang et al. for the copper-catalyzed trifluoromethylati...
Figure 9: Mechanistic rationale for the trifluoromethylation of arenes in presence of Langlois’s reagent and ...
Scheme 7: Trifluoromethylation of 4-acetylpyridine with Langlois’s reagent by P. S. Baran et al. (* Stirring ...
Scheme 8: Catalytic copper-facilitated perfluorobutylation of benzene with C4F9I and benzoyl peroxide [90].
Figure 10: F.-L. Qing et al.’s proposed mechanism for the copper-catalyzed trifluoromethylation of (hetero)are...
Figure 11: Mechanism of the Cu-catalyzed/Ru-photocatalyzed trifluoromethylation and perfluoroalkylation of ary...
Figure 12: Proposed mechanism for the Cu-catalyzed trifluoromethylation of aryl- and vinyl boronic acids with ...
Figure 13: Possible mechanism for the Cu-catalyzed decarboxylative trifluoromethylation of cinnamic acids [62].
Scheme 9: Ruthenium-catalyzed perfluoroalkylation of alkenes and (hetero)arenes with perfluoroalkylsulfonyl c...
Figure 14: N. Kamigata et al.’s proposed mechanism for the Ru-catalyzed perfluoroalkylation of alkenes and (he...
Figure 15: Proposed mechanism for the Ru-catalyzed photoredox trifluoromethylation of (hetero)arenes with trif...
Figure 16: Late-stage trifluoromethylation of pharmaceutically relevant molecules with trifluoromethanesulfony...
Figure 17: Proposed mechanism for the trifluoromethylation of alkenes with trifluoromethyl iodide under Ru-bas...
Scheme 10: Formal perfluoroakylation of terminal alkenes by Ru-catalyzed cross-metathesis with perfluoroalkyle...
Figure 18: One-pot Ir-catalyzed borylation/Cu-catalyzed trifluoromethylation of complex small molecules by Q. ...
Figure 19: Mechanistic proposal for the Ni-catalyzed perfluoroalkylation of arenes and heteroarenes with perfl...
Scheme 11: Electrochemical Ni-catalyzed perfluoroalkylation of 2-phenylpyridine (Y. H. Budnikova et al.) [71].
Scheme 12: Fe(II)-catalyzed trifluoromethylation of arenes and heteroarenes with trifluoromethyl iodide (T. Ya...
Figure 20: Mechanistic proposal by T. Yamakawa et al. for the Fe(II)-catalyzed trifluoromethylation of arenes ...
Scheme 13: Ytterbium-catalyzed perfluoroalkylation of dihydropyran with perfluoroalkyl iodide (Y. Ding et al.) ...
Figure 21: Mechanistic proposal by A. Togni et al. for the rhenium-catalyzed trifluoromethylation of arenes an...
Figure 22: Mechanism of the Cu-catalyzed oxidative trifluoromethylthiolation of arylboronic acids with TMSCF3 ...
Scheme 14: Removal of the 8-aminoquinoline auxiliary [136].
Figure 23: Mechanism of the Cu-catalyzed trifluoromethylthiolation of C–H bonds with a trifluoromethanesulfony...
Trifluoromethyl ethers – synthesis and properties of an unusual substituent
- Frédéric R. Leroux,
- Baptiste Manteau,
- Jean-Pierre Vors and
- Sergiy Pazenok
Beilstein J. Org. Chem. 2008, 4, No. 13, doi:10.3762/bjoc.4.13
Graphical Abstract
Figure 1: OCF3-bearing pesticides.
Scheme 1: Preparation of trifluoromethyl ethers via a chlorination/fluorination sequence.
Scheme 2: Preparation of trifluoromethyl ethers via an in situ chlorination/fluorination sequence.
Scheme 3: Preparation of trifluoromethyl ethers via chlorothionoformates.
Scheme 4: Preparation of trifluoromethyl ethers via fluoroformates.
Scheme 5: Oxidative desulfurization-fluorination toward trifluoromethyl ethers.
Scheme 6: Mechanism of the oxidative desulfurization-fluorination.
Scheme 7: Umemoto's O-(trifluoromethyl)dibenzofuranium salts 4 as CF3-transfer agents.
Scheme 8: Togni's approach using hypervalent iodine compounds as CF3-transfer agents.
Scheme 9: TAS OCF3 as a nucleophilic OCF3-transfer agent.
Figure 2: Mesomeric structures of the OCF3-group.
Figure 3: Structures of 6 and 7.
Figure 4: Conformational preference of the trifluoromethoxy group on aryl rings.
Scheme 10: Nitration of trifluoromethoxy benzene.
Scheme 11: Synthesis and Nitration of N-Acetyl-(trifluoromethoxy)anilines.
Scheme 12: Bromine/lithium exchange of bromo(trifluoromethoxy)benzenes.
Scheme 13: Metalation of (trifluoromethoxy)benzene.
Scheme 14: Metalation of (trifluoromethoxy)naphthalenes.
Scheme 15: Competition between -CF3- and -OCF3 in Metalation reactions.
Scheme 16: Competition between -F- and -OCF3 in Metalation reactions.
Scheme 17: Metalation of trifluoromethoxyanisoles.
Figure 5: Direction of π-polarization depending on the substituent as described by Schlosser et al. [57].
Scheme 18: Metalation of Bromo(trifluoromethoxy)benzenes.
Scheme 19: Aryne formation from bromo(trifluoromethoxy)phenyllithiums and subsequent Diels-Alder cycloaddition...
Scheme 20: Metalation of (trifluoromethoxy)anilines.
