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1. Regioreversed Carbosulfenylation of Fluoroalkenes via Nickel‐Mediated Radical Sorting

   https://doi.org/10.1002/anie.202509664  

   Zhu, Chuan; Liu, Qian; Wang, Nannan; Ma, Rui; Chen, Kai; Walsh, Patrick_J; Guo, Kai; Feng, Chao (June 2025, Angewandte Chemie International Edition)

   Abstract Carbosulfenylation of olefins represents an important class of reactions for the synthesis of structurally diverse organosulfur compounds. Previous studies typically yield 1,2‐regioselectivity. In the context of diversity‐oriented synthesis, accessing the regioreversed products is desirable, significantly broadening the scope of these reactions. In this study, we report a nickel‐catalyzed 2,1‐carbosulfenylation of trifluoromethyl‐ andgem‐difluoroalkenes, using free thiols and benzyl bromides as sulfur and carbon sources, respectively. The unusual regioselectivity observed is enabled by a “radical sorting” mechanism. The Ni catalyst activates benzyl bromide to generate a benzylic radical that undergoes hydrogen atom transfer (HAT) with the thiol to form a sulfur‐centered radical. The sulfur radical subsequently adds to the fluoroalkenes, resulting in an α‐fluoroalkyl C‐radical. This radical undergoes S_H2 with a Ni–CH₂Ar to form a C(sp³)─C(sp³) bond and quaternary center, ultimately producing valuable fluoroalkyl thioethers. Isotopic labeling experiments corroborate a hydrogen atom transfer (HAT) event within the working mechanism. 

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2. Cascade Defluorination of Perfluoroalkylated Catholytes Unlocks High Lithium Primary Battery Capacities

   https://doi.org/10.1002/aenm.202301751  

   Gao, Haining; Yoshinaga, Kosuke; Steinberg, Katherine; Swager, Timothy_M; Gallant, Betar_M (July 2023, Advanced Energy Materials)

   Abstract Exceeding the energy density of lithium−carbon monofluoride (Li−CF_x), today's leading Li primary battery, requires an increase in fluorine content (x) that determines the theoretical capacity available from C−F bond reduction. However, high F‐content carbon materials face challenges such as poor electronic conductivity, low reduction potentials (<1.3 V versus Li/Li⁺), and/or low C−F bond utilization. This study investigates molecular structural design principles for a new class of high F‐content fluoroalkyl‐aromatic catholytes that address these challenges. A polarizable conjugated system—an aromatic ring with an alkene linker—functions as electron acceptor and redox initiator, enabling a cascade defluorination of an adjacent perfluoroalkyl chain (R_F= −C_nF_2n+1). The synthesized molecules successfully overcome premature deactivation observed in previously studied catholytes and achieve close‐to‐full defluorination (up to 15/17 available F), yielding high gravimetric capacities of 748 mAh g⁻¹_{fluoroalkyl‐aromatic}and energies of 1785 Wh kg⁻¹_{fluoroalkyl‐aromatic}. The voltage compatibility between fluoroalkyl‐aromatics and CF_xenables design of hybrid cells containing C−F redox activity in both solid and liquid phases, with a projected enhancement of Li–CF_xgravimetric energy by 35% based on weight of electrodes+electrolyte. With further improvement of cathode architecture, these “liquid CF_x” analogues are strong candidates for exceeding the energy limitations of today's primary chemistries. 

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3. Phosphorus-mediated sp2-sp3 couplings for C–H fluoroalkylation of azines

   https://doi.org/10.1038/s41586-021-03567-3  

   Zhang, Xuan; Nottingham, Kyle G.; Patel, Chirag; Alegre-Requena, Juan V.; Levy, Jeffrey N.; Paton, Robert S.; McNally, Andrew (April 2021, Nature)

   null (Ed.)

   Fluoroalkyl groups profoundly affect the physical properties of pharmaceuticals and influence virtually all metrics associated with their pharmacokinetic and pharmacodynamic profiles. Drug candidates increasingly contain CF3 and CF2H groups, and the same trend in agrochemical development shows that the effect of fluoroalkylation translates across human, insect, and plant life. New fluoroalkylation reactions have undoubtedly stimulated this uptake; however, methods that directly convert C–H bonds into C–CF2X (X = F or H) groups in complex drug-like molecules are rare. For pyridine, the most common aromatic heterocycle in pharmaceuticals, only one approach, via fluoroalkyl radicals, is viable for pyridyl C–H fluoroalkylation in the elaborate structures encountered during drug development. Here, we have developed a set of bench-stable fluoroalkylphosphines that directly convert the C–H bonds in pyridine building blocks, drug-like fragments, and pharmaceuticals into fluoroalkyl derivatives. No pre-installed functional groups or directing groups are required; the reaction tolerates a variety of sterically and electronically distinct pyridines and is exclusively selective for the 4-position in most cases. The reaction proceeds via initial phosphonium salt formation followed by sp2-sp3 phosphorus ligand-coupling, an underdeveloped manifold for C–C bond formation. 

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4. Fluorous Metal–Organic Frameworks and Nonporous Coordination Polymers as Low‐κ Dielectrics

   https://doi.org/10.1002/adfm.201904707  

   Galli, Simona; Cimino, Alessandro; Ivy, Joshua_F; Giacobbe, Carlotta; Arvapally, Ravi_K; Vismara, Rebecca; Checchia, Stefano; Rawshdeh, Mustafa_A; Cardenas, Christian_T; Yaseen, Waleed_K; et al (August 2019, Advanced Functional Materials)

   Abstract A fluorous metal–organic framework [Cu(FBTB)(DMF)] (FMOF‐3) [H₂FBTB = 1,4‐bis(1‐H‐tetrazol‐5‐yl)tetrafluorobenzene] and fluorous nonporous coordination polymer [Ag₂(FBTB)] (FN‐PCP‐1) are synthesized and characterized as for their structural, thermal, and textural properties. Together with the corresponding nonfluorinated analogues lc‐[Cu(BTB)(DMF)] and [Ag₂(BTB)], and two known (super)hydrophobic MOFs, FMOF‐1 and ZIF‐8, they have been investigated as low‐dielectric constant (low‐κ) materials under dry and humid conditions. The results show that substitution of hydrogen with fluorine or fluoroalkyl groups on the organic linker imparts higher hydrophobicity and lower polarizability to the overall material. Pellets of FMOF‐1, FMOF‐3, and FN‐PCP‐1 exhibit κ values of 1.63(1), 2.44(3), and 2.57(3) at 2 × 10⁶Hz, respectively, under ambient conditions, versus 2.94(8) and 3.79(1) for lc‐[Cu(BTB)(DMF)] and [Ag₂(BTB)], respectively. Such low‐κ values persist even upon exposure to almost saturated humidity levels. Correcting for the experimental pellet density, the intrinsic κ for FMOF‐1 reaches the remarkably low value of 1.28, the lowest value known to date for a hydrophobic material. 

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5. Ligand‐to‐Metal Charge Transfer of Ag(II) CF ₂ X Carboxylates: Quantum Yield and Electrophotocatalytic Arene Fluoroalkylation Tuned by X

   https://doi.org/10.1002/anie.202511642  

   Campbell, Brandon_M; Gordon, Jesse_B; Raguram, Elaine_Reichert; Reynolds, Kristopher_G; Sullivan, Meghan_G; Nocera, Daniel_G (September 2025, Angewandte Chemie International Edition)

   Abstract Incorporation of CF₂X groups beyond CF₃into arene scaffolds is underdeveloped despite these groups’ utility as halogen‐bond donors and as precursors to bioisosteres. Herein, we report the synthesis, characterization, and comparative photochemistry of a suite of [Ag(II)(bpy)₂O₂CCF₂X]⁺and Ag(II)(bpy)(O₂CCF₂X)₂(bpy = 2,2´‐bipyridine, X = F, CF₃, Cl, Br, H, CH₃) carboxylate complexes. We find a dramatic effect of the X substituent on the efficiency of generating CF₂X radicals by ligand‐to‐metal charge transfer (LMCT), with Ag(II) photoreduction rates varying by over an order of magnitude and quantum yields spanning over 20%. We provide insight into how electronic and structural perturbations of the Ag(II)–O₂CCF₂X core are manifested in the LMCT quantum efficiency. With this information in hand, Ag(II)‐mediated electrophotocatalytic CF₂X functionalization is carried out on a range of (hetero)arenes. This work expands the nascent field of Ag(II)‐based photocatalysis by allowing for (hetero)aryl–CF₂X functionalization directly from unactivated fluoroalkyl carboxylate precursors. 

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