Copper-catalyzed electrochemical C–H fluorination

Hintz, Heather A.; Bower, Jamey K.; Tang, Jinghua; LaLama, Matthew; Sevov, Christo S.; Zhang, Shiyu

doi:10.1016/j.checat.2022.100491

Cited by 21 publications

(16 citation statements)

References 54 publications

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“…In spite of its thermal instability, 35 was characterized by 1 H NMR analysis, UV‐vis and Sc‐XRD. In this first contribution, [49a] the proficiency of 35 in stoichiometric C(sp 3 )−H fluorination was demonstrated for a small array of substrates (7 examples; Figure 11 top), whilst a later contribution by the same group proved 35 to be catalytically competent for the electrochemical fluorination of aliphatic C−H bonds (Figure 11 bottom) [49b] . This represents the first undeniable evidence for the involvement of Cu III −F species in catalytic fluorination.…”

Section: Cross‐coupling Enabled By Agi/agiii Redox Sequencesmentioning

confidence: 82%

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Demonti

Joven-Sancho

Nebra

2023

The Chemical Record

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AgIII compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement of Ag catalysts in cross‐coupling via 2e− redox sequences is frequently discarded. Nevertheless, organosilver(III) compounds have been authenticated using tetradentate macrocycles or perfluorinated groups as supporting ligands, and since 2014, first examples of cross‐coupling enabled by AgI/AgIII redox cycles saw light. This review collects the most relevant contributions to this field, with main focus on aromatic fluorination/perfluoroalkylation and the identification of AgIII key intermediates. Pertinent comparison between the activity of AgIIIRF compounds in aryl‐F and aryl‐CF3 couplings vs. the one shown by its CuIIIRF and AuIIIRF congeners is herein disclosed, thus providing a more profound picture on the scope of these transformations and the pathways commonly associated to C−RF bond formations enabled by coinage metals.

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Section: Cross‐coupling Enabled By Agi/agiii Redox Sequencesmentioning

confidence: 82%

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Demonti

Joven-Sancho

Nebra

2023

The Chemical Record

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“…29−32 Zhang's group isolated Cu III −X (X = F − , Cl − and Br − ) complexes and utilized the Cu III −F complex as an electrochemical catalyst for C−H fluorination via an oxidative asynchronous PCET process. 33,34 Lacy and co-workers established the thermodynamics of Mn− Cl bond homolysis related to predictive C−H bond reactivity. 35 However, mononuclear transition-metal halide complexes with oxidation states higher than 4+ have been rarely reported so far.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Reactivity of a Highly Oxidative Mononuclear Manganese(IV)–Bis(Fluoro) Complex

Jeong,

Lee,

Lee

et al. 2024

J. Am. Chem. Soc.

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Recently, transition-metal terminal nonoxo complexes have shown a remarkable ability to activate and functionalize C−H bonds via proton-coupled electron transfer (PCET). Here we report the first example of a mononuclear manganese(IV) bis(fluoro) complex bearing a tetradentate pyridinophane ligand, [Mn IV (TBDAP)(F) 2 ] 2+ (3), with an X-ray single crystal structure and physicochemical characterization. The manganese(IV) bis(fluoro) complex has a very high reduction potential of 1.61 V vs SCE, thereby enabling the four-electron oxidation of mesitylene to 3,5-dimethylbenzaldehyde. Kinetic studies, including the kinetic isotope effect and employment of other toluene derivatives, reveal the electron transfer (ET)-driven PCET in the C−H bond activation of mesitylene by 3. This novel metal halide intermediate would be prominently valuable for expanding transition-metal halide chemistry.

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“…Nonheme iron complexes with tetradentate nitrogen donor ligands have been used similarly to convert R–H bonds into R–OH or R–Cl bonds via rebound from a putative Fe III (OH)(halide) intermediate. , It is the rebound step that is thought to determine product selectivity. Nonheme copper, nickel, and manganese complexes also mediate analogous radical transfer chemistry, although in some cases a “non-oxo” radical relay strategy is employed, where R–H bond cleavage is carried out by a secondary oxidant instead of a high-valent metal-oxo intermediate, which is then followed by radical transfer from M–X to R • to give R–X products. – This strategy was recently used with a nonheme iron enzyme to provide a biocatalytic platform for C–H azidation and is a promising method for the functionalization of C–H bonds by first-row transition metals.…”

Section: Introductionmentioning

confidence: 99%

Selective Radical Transfer in a Series of Nonheme Iron(III) Complexes

Yadav,

Wen,

Yadav

et al. 2023

Inorg. Chem.

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A series of nonheme iron complexes, FeIII(BNPAPh2O)(Lax)(Leq) (Lax/eq = N3 –, NCS–, NCO–, and Cl–) have been synthesized using the previously reported BNPAPh2O– ligand. The ferrous analogs FeII(BNPAPh2O)(Lax) (Lax = N3 –, NCS–, and NCO–) were also prepared. The complexes were structurally characterized using single crystal X-ray diffraction, which shows that all the FeIII complexes are six-coordinate, with one anionic ligand (Lax) in the H-bonding axial site and the other anionic ligand (Leq) in the equatorial plane, cis to the Lax ligand. The reaction of FeIII(BNPAPh2O–)(Lax)(Leq) with Ph3C• shows that one ligand is selectively transferred in each case. A selectivity trend emerges that shows •N3 is the most favored for transfer in each case to the carbon radical, whereas Cl• is the least favored. The NCO and NCS ligands showed an intermediate propensity for radical transfer, with NCS > NCO. The overall order of selectivity is N3 > NCS > NCO > Cl. In addition, we also demonstrated that H-bonding has a small effect on governing product selectivity by using a non-H-bonded ligand (DPAPh2O–). This study demonstrates the inherent radical transfer selectivity of nonhydroxo-ligated nonheme iron(III) complexes, which could be useful for efforts in synthetic and (bio)catalytic C–H functionalization.

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Copper-catalyzed electrochemical C–H fluorination

Cited by 21 publications

References 54 publications

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Synthesis, Characterization, and Reactivity of a Highly Oxidative Mononuclear Manganese(IV)–Bis(Fluoro) Complex

Selective Radical Transfer in a Series of Nonheme Iron(III) Complexes

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