Herein we report the use of photoredox and organic catalysis to accomplish the C(sp3)-H amination of unactivated olefins with sulfonamides, enabling efficient access to allylic amine products with high E-selectivity. The protocol does not require a metal catalyst or prefunctionalization of the coupling partners, and it features mild conditions and functional group tolerance as evidenced by >60 examples. A preliminary mechanistic study uncovered that the transformation involved radical-radical coupling of an allylic radical with a N-centered radical under visible light irradiation.

The stereodivergent coupling via photoredox/transition metal catalysis has emerged as a powerful tool to construct diverse alkenes in both E and Z configurations. Despite well-established catalytic systems involving late transition metals, the early transition metal catalyzed stereodivergent synthesis of alkenes still remains underdeveloped. Herein in this work, a stereodivergent reductive C(sp2)-C(sp3) coupling between cycloketone oximes and vinyl halides has been achieved by tunable photoredox/Ti dual catalysis, providing a facile access to a broad scope of cyano-substituted (fluoro)alkenes with high efficiency and controlled E/Z selectivity. Several products exhibited promising antifungal activities.

Herein, we report a photochemical C-H methylation and silylation of heteroarenes through the combination of visible light and N-fluorobenzenesulfonimide (NFSI). This practical method allows for the incorporation of a methyl or silyl group, produced from methanol and hydrosilane, into heteroarene architectures in a photocatalyst- and metal-free fashion. Mechanistic investigation suggests that the N-centered radical, generated from homolysis of the N-F bond in NFSI, plays a critical role by abstracting a hydrogen atom from a C-H or Si-H bond.

A photoredox/Ti dual‐catalyzed deoxygenative coupling reaction between Morita–Baylis–Hillman acetates and unprotected cycloketone oximes has been developed. A broad range of cyano‐containing trisubstituted alkenes have been expediently synthesized in good chemo‐ and stereo‐selectivities under very mild conditions. Mechanistic experiments, scale‐up reaction, and functionalization of complex molecules were conducted, in order to showcase the mechanistic features and robustness of this protocol.

Natural products serve as a vital source of compounds for the development of novel agricultural antifungal agents. In this study, a series of novel l-perillyl alcohol amide/hydrazide derivatives containing a piperazine moiety were designed and synthesized using l-perillyl alcohol as the structural scaffold. In vitro bioactivity assays demonstrated that most of the target compounds exhibited significant antifungal activity. Notably, compound F2 displayed broad-spectrum antifungal potency, with EC50 values of 0.212, 2.35, 4.76, 2.31, and 1.90 μg/mL against Rhizoctonia solani, Valsa mali, Botrytis cinerea, Alternaria solani, and Sclerotinia sclerotiorum, respectively. Further in vivo evaluations confirmed that compound F2 exhibited favorable protective efficacy against R. solani, A. solani, and S. sclerotiorum, highlighting its potential as a novel agricultural antifungal agent. Mechanistic studies demonstrated that the antifungal activity of compound F2 against R. solani is achieved by disrupting the normal morphology and cellular structure of hyphae, increasing cell membrane permeability, inducing the generation and accumulation of reactive oxygen species, and impairing mitochondrial function, which ultimately inhibits the growth and proliferation of hyphae. Moreover, succinate dehydrogenase (SDH) enzymatic activity assays and molecular dynamic simulations further confirmed that compound F2 shares a highly analogous action mechanism and binding mode to SDH with boscalid. These findings offer valuable insights for developing novel SDH-inhibiting fungicides.

To develop novel fungicidal agents, 40 novel maltol-based derivatives were designed, synthesized, and evaluated for antifungal activity. Most compounds exhibited potent in vitro efficacy against phytopathogenic fungi, with A2, A3, A4, A8, A9, A23, A24, and A25 showing strong activity against Rhizoctonia solani. Moreover, compound A2 exerted broad-spectrum antifungal effects against six phytopathogenic fungi. In vivo antifungal activities of compound A24 against Rhizoctonia solani and Botrytis cinerea highlighted its potential in crop protection. Propidium iodide (PI) staining and cellular content release assays indicated that compound A24 disrupted the membrane integrity, thereby inhibiting the mycelial growth and proliferation. Microscopic observations revealed that compound A24 caused irregular morphological alterations in the mycelia and cellular structures. Moreover, compound A24 induced mitochondrial dysfunction, confirmed by mitochondrial membrane potential (MMP) analysis. Succinate dehydrogenase (SDH) enzyme activity assays and molecular docking studies further demonstrated that compound A24 holds considerable promise as a novel SDHI fungicide.

Reported herein is a photoredox/cobaloxime dual-catalytic approach to execute tandem dehydrogenative azolation and aromatization of tetrahydronaphthalene for rapid construction of N-(β-naphthyl)azole architectures. This protocol highlights noble metal-free and external oxidants-free conditions, step- and atom-economy, and site-selectivity. A preliminary mechanistic study has uncovered that the transformation undergoes a N-centered radical mediated C-H/N-H cross-coupling followed by dehydrogenative aromatization of saturated naphthyl surrogates under visible light irradiation, and DFT calculations elucidate the site-selectivity.

In this study, 36 novel hydrazide-containing L-perillaldehyde derivatives were designed, synthesized, and evaluated for their antifungal activity. In the in vitro antifungal assays, most of the target compounds exhibited remarkable antifungal activity. Notably, compound C4 displayed exceptional antifungal activities against Rhizoctonia solani (EC50 = 0.260 μg/mL), Fusarium graminearum (EC50 = 0.480 μg/mL), Sclerotinia sclerotiorum (EC50 = 0.240 μg/mL), and Valsa mali (EC50 = 0.512 μg/mL), outperforming carbendazim, which showed EC50 values of 0.651, 0.804, 0.520, and 0.898 μg/mL, respectively. Meanwhile, in vivo assays against R. solani and S. sclerotiorum revealed compound C4's potential as a novel agricultural antifungal agent. In the investigation of the antifungal mechanism, scanning electron microscopy and transmission electron microscopy observations revealed that compound C4 induced significant morphological alterations in R. solani mycelia, including mitochondrial swelling and rupture, thereby inhibiting mycelial growth. Determination of cellular content leakage and propidium iodide (PI) staining experiments indicated that compound C4 compromised the integrity of the R. solani cell membrane, leading to cytoplasmic efflux and, subsequently, inhibiting normal mycelial development. The detection of reactive oxygen species indicated that the antifungal activity of compound C4 may stem from inducing accumulation of reactive oxygen species within cells. The mitochondrial membrane potential detection demonstrated that compound C4 could decrease the mitochondrial membrane potential, thereby damaging mitochondria. Furthermore, compound C4 (IC50 = 14.5 μg/mL) exhibited potent succinate dehydrogenase (SDH) inhibitory activity comparable to that of boscalid (IC50 = 12.6 μg/mL). Molecular dynamics simulations confirmed that compound C4 could establish strong interactions with key residues of SDH. These results offer significant insights and guidance for the development of novel antifungal agents.

A Brønsted acid enabled metal-free remote functionalization of NHPI esters via 1,4-group migration chaperoned radical-polar crossover has been established, affording a variety of alcohols, ethers and amides in moderate to good yields.

In this work, a total of 45 novel isophorone derivatives were designed, synthesized, and evaluated for antifungal activity against six phytopathogenic fungi. Some target compounds displayed remarkable and broad-spectrum antifungal activities in vitro against tested phytopathogenic fungi. Among them, compound A2 exhibited excellent antifungal activity against Rhizoctonia solani, Sclerotinia sclerotiorum, Valsa mali, Botrytis cinerea, Gibberella zeae, and Physalospora piricola, with the corresponding EC50 values of 0.133, 0.258, 0.428, 0.519, 1.29, and 1.51 μg/mL, respectively. Additionally, results from in vivo experiments indicated that compound A2 could function as a novel antifungal candidate for safeguarding agricultural crops against fungal infections. During the investigation into the antifungal mechanism, the cell membrane permeability and propidium iodide (PI) staining experiments demonstrated that compound A2 could destroy the cell membrane structure and increase the permeability of the cell membrane. Findings from microscopic observations, in tandem with mitochondrial membrane potential (MMP) detection, revealed that compound A2 severely damaged the structural integrity of cells. Concurrently, compound A2 decreased the MMP, thereby inducing cell apoptosis and inhibiting the normal growth of mycelia. Moreover, results from succinate dehydrogenase (SDH) enzyme assays, molecular dynamics (MD) simulations, and molecular docking experiments further indicated that compound A2, Thifluzamide, and boscalid might have similar mechanisms of action and binding modes with SDH. Finally, to investigate the structural basis for differences in bioactivity, the frontier molecular orbitals and molecular electrostatic potential were calculated. The outcomes of this work significantly contribute to further research aimed at agricultural plant disease control.

Reported herein is an electrochemical strategy for N-sulfonylation of azoles with sulfonyl hydrazides, offering efficient access to valuable N-sulfonated azoles. Organic radical species were involved in the process and EPR experiments provided evidence for the formation of intermediates in situ. The electrochemical reaction features metal-free, mild conditions, and a broad substrate scope (>70 examples). The gram-scale synthesis via an electrochemical continuous-flow reaction and late-stage modification of complex compounds is advocated for its practical value.

A photoredox/Cu dual catalyzed 1,4-cyanosulfonylation of NHPI esters with readily available sodium arylsulfinates has been established under mild conditions, which provides an expedient approach to a variety of δ-sulfonyl nitriles...

Reported herein is direct C(sp3)-H arylation of unprotected benzyl anilines and alkylarenes via consecutive photoinduced electron transfer by visible light irradiation. Reductive quenching cycles and radical-radical cross-coupling were involved, and electron paramagnetic resonance experiments provide evidence for the formation of radical intermediates formed in situ. The protocol highlights transition metal free, external oxidant free, broad substrate scope, and high efficiency (>60 examples, up to 96%).

A silver-catalyzed decarboxylative remote fluorination via a zwitterion-promoted 1,4-heteroaryl migration has been developed. A variety of heteroaryl-tethered benzyl fluorides have been readily synthesized with good regioselectivity under mild conditions. The zwitterion of the substrate is suggested to accelerate the 1,4-heteroaryl migration, which determines the regioselectivity of this transformation.

A dehydroxylative ring-opening Giese reaction of cyclobutanone oximes enabled by photoredox/Ti dual catalysis has been reported in this work. This protocol avoids the prefunctionalization of oximes and the use of stoichiometric triarylphosphine reagents. It also features mild conditions, broad substrate scope and good functional group tolerance. The gram-scale reaction, product derivatization, late-stage functionalization of complex pharmaceutical and natural product derivatives, and oligopeptide modification exhibit the potential application of this methodology in synthetic chemistry.

A visible light-induced transition metal-free benzylic C(sp(3))-C(sp(2)) defluorinative coupling between indole derivatives and polyfluoroarenes via the sequential electron transfer-proton transfer (ET/PT) process has been developed, affording various polyfluorinated diarylmethanes. This protocol features mild conditions and good functional group tolerance.

Sulfonyl‐tethered N ‐containing heterocycles are valuable building blocks in synthetic and pharmaceutical chemistry. Recently, the installation of fluoroalkanesulfonyl groups into heterocycles via the difunctionalization of alkenes still remains challenging. Herein in this work, an imino‐fluoroalkanesulfonylation of γ,δ‐unsaturated oxime esters has been achieved via photoredox/Cu dual catalysis. A variety of fluoroalkanesulfonyl‐tethered pyrroline derivatives have been readily synthesized in moderate to good yields under mild conditions.

A photoinduced copper-catalyzed enantioconvergent remote alkynylation of N-hydroxyphthalimide esters with terminal alkynes via 1,4-heteroaryl migration has been developed. A broad scope of heteroaryl-tethered chiral alkynes has been synthesized with good regio- and enantioselectivities. The chiral-ligand-coordinated copper species plays a dual role as both the photoredox and cross-coupling catalyst. This methodology provides a new platform for enantioconvergent remote alkynylations.

A photoredox catalyzed trifluoromethyl radical-triggered trifunctionalization of 5-hexenenitriles via cyano group migration is reported. The cyano group migration is of high chemo-selectivity even in the presence of aryl or heteroaryl groups as competitors. This protocol provides a facile access to a broad scope of CF3-containing compounds with high molecular complexity and functional group diversity. The success of gram-scale reaction and the versatility of products in derivative synthesis illustrate the potential value of this transformation in synthetic chemistry.