A thermally stable, light-insensitive crystalline fluorosulfonyl tetrafluoroethoxylating reagent, [(Ph3P)Ag(OCF2CF2SO2F)]2 (1), was developed. The reagent demonstrates high nucleophilicity toward diverse electrophiles, including benzyl bromides/chlorides, alkyl bromides, triflates, and secondary alkyl nosylates. The incorporated sulfonyl fluoride moiety demonstrates remarkable versatility, undergoing facile conversion to both sulfonates and sulfones through reactions with various nucleophiles. Furthermore, we have successfully applied this chemistry to prepare a series of photoacid generators with potential applications in photolithography technology.

Palladium-catalyzed fluorocarbonylation of iodoarenes using difluoromethyl benzoate (DFBz) or difluoromethyl p-cyano-benzoate (DFBz-CN) as a fluorocarbonylation reagent has been developed, affording structurally diverse acyl fluorides as products. Both DFBz and DFBz-CN reagents are conveniently prepared through insertion of difluorocarbene into the O-H bonds of carboxylic acids. The activation of these two difluoromethyl benzoates with CsF generates formyl fluoride (HCOF), which readily decomposes into CO and HF. Therefore, both DFBz and DFBz-CN can be successfully used as safe surrogates of CO. This study provides not only a new synthetic method for fluorocarbonylation but also intriguing insights into the different reactivity between the previously known trifluoromethyl benzoate (TFBz, an effective CF3O- synthon) and the currently studied difluoromethyl benzoate (DFBz, not a satisfactory HCF2O- synthon).

Based on our previous discovery that alkyl-side-chains in the aryl polymers have a positive effect on dielectric properties of the polymers, this work further investigates the side-chain effect by a hydrogenated bio-based cardanol monomer with a long pentadecyl alkyl side chain. The monomer was functionalized by introducing the thermocrosslinkable benzocyclobutene groups, and its cured product displayed a dielectric constant (e) of 2.59 and a dielectric loss (tan delta) of 5 x 10- 4 at a high frequency of 10 GHz. In contrast, a controlling polymer with methyl side chain exhibited a epsilon of 2.84 and a tan delta of 1.4 x 10-3, respectively. Such data indicate that the long alkyl-side-chains can effectively improve the dielectric properties of the aryl polymers. Moreover, the cured hydrogenated bio-based cardanol also exhibited good hydrophobicity properties with the water absorption of 0.16 % even immersing it in boiling water for 96 h. These results imply that bio-based cardanol is a potential candidate for the preparation of the low-k materials used in microelectronic industry.

While most reported Co(-I) complexes are coordinatively saturated, we report herein a 16e- Co(-I) complex [(cyIDep)Co(eta 2-vtms)(N2)Na(OEt2)]2 (where cyIDep = 1,3-di(2 ',6 '-diethylphenyl)-4,5-(CH2)4-imidazol-2-ylidene; and vtms = vinyltrimethylsilane). The Co(-I) complex is isolated from the reaction of [(cyIDep)Co(eta 2-vtms)2] with sodium under a dinitrogen atmosphere. It features short Co-N (1.695(3)/1.695(3) & Aring;) and long N-N bonds (1.166(4)/1.168(3) & Aring;). Theoretical study indicates the presence of 2-fold Co-to-N2 pi-backdonation interactions in the three-coordinate Co(-I) species, which might lead to thermodynamic gains to the unusual alkene-to-N2 ligand exchange reaction that gives the Co(-I) complex. The attempts to functionalize the dinitrogen ligand in the Co(-I) complex with Me3SiCl and a N-heterocyclic silylene lead to the isolation of the cobalt(I) alkyl complex [(cyIDep)Co(C(SiMe3)2Me)] and the cobalt(0) complex [( t-BuNHSi)(cyIDep)Co(eta 2-vtms)] ( t-BuNHSi = 1,3-bis(tert-butyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene), respectively, rather than the desired products.

This study presents a strategy utilizing difluorocarbene as a dual C-1/CF2 source for the efficient synthesis of HCF2S-substituted six-membered aromatic heterocycles. The in situ generation of thiocarbonyl fluoride (S=CF2) from the reaction of readily available difluorocarbene reagent Ph3P+CF2CO2- (PDFA) with elemental sulfur enables the simultaneous cyclization and difluoromethylthiolation of substrates containing vicinal nucleophilic groups (amide or carboxyl) and amines. This method provides rapid access to quinazolinone and benzoxazinone scaffolds bearing the biologically relevant difluoromethylthio group under mild conditions, demonstrating a broad substrate scope and functional group compatibility. The work highlights the versatility of difluorocarbene in constructing valuable fluorinated heterocycles with potential applications in medicinal and agrochemical chemistry.

Artificial photoenzymes hold transformative potential for in vitro biocatalysis, but their translation to live-cell environments demands minimal cellular perturbation and aerobic compatibility. Here, we present miniSOG, a 12 kDa miniature photoenzyme that enables bioorthogonal deboronative hydroxylation via superoxide radical anion (O2 center dot-) generation under blue light irradiation. Leveraging the inherent photochemistry of flavins, miniSOG facilitates the photoactivation of 27 structurally diverse organoboronates-including aryl/alkyl boronates, fluorophores, anticancer agents, and epigenetic modulators-through a unified O2 center dot--mediated mechanism. This system achieves spatiotemporally precise photocatalysis in live cells, where miniSOG's compact size and subcellular targeting enable organelle-specific localization and confined reactivity due to short-range O2 center dot- diffusion (similar to 0.2 mu m). We demonstrate its utility in light-gated cellular modulation: i) mitochondrial depolarization via localized release of 2,4-dinitrophenol (DNP) to disrupt energy metabolism, and ii) nuclear m6A methylation enhancement to epigenetically upregulate autophagy. By repurposing miniSOG's photochemistry for bioorthogonal deboronative hydroxylation, this work establishes a versatile, genetically encoded platform for manipulating fundamental cellular pathways with minimal off-target effects.