Yunhe Jin

Phosphonium salts are valuable intermediates in organic synthesis, but their preparation often requires harsh conditions and specific carbon precursors. Herein, we report a photoinduced decarboxylative phosphoniumation of redox-active esters (RAEs) for the direct synthesis of alkyl and benzyl phosphonium salts. A photoresponsive ternary charge-transfer complex (CTC) formed from NaI, tertiary phosphines, and RAEs enables the reaction under transition-metal- and external-photocatalyst-free conditions. The method tolerates diverse benzyl and aliphatic RAEs and tertiary phosphines, including commercial phosphine ligand frameworks, and enables the late-stage phosphoniumation of complex carboxylic-acid-derived substrates.

Alkene carbothiolation enables simultaneous construction of C–C and C–S bonds yet remains challenging for the synthesis of thioethers because low-valent sulfur species readily coordinate to and deactivate transition metal catalysts. Herein, we report a photoinduced Fe/Ni dual-catalytic system that achieves alkene carbothiolation through direct C(sp³)–H activation of simple alkanes. From the merger of ligand-to-metal charge transfer (LMCT)-enabled alkyl radical generation with nickel-catalyzed cross-coupling/sulfide oxidation state modulation, this strategy enables efficient installation of both carbon and sulfur functionalities across alkenes while bypassing the need for prefunctionalized radical precursors. The method provides straightforward access to structurally diverse thioethers from abundant hydrocarbon feedstocks and exhibits broad functional group tolerance and good scalability.

Sulfoxides occupy a central role in natural products and bioactive molecules, yet their direct construction from simple feedstocks remains challenging. Herein, we report a dual iron/nickel photocatalytic strategy for the selective C(sp³)-H sulfoxidation of liquid/gaseous alkanes using industrially abundant aryl sulfonyl chlorides. Broad substrate scope, good functional group tolerance, operational simplicity, high chemoselectivity, scale-up synthesis, and late-stage modification are demonstrated, providing a practical platform for the preparation of high-value sulfur-containing compounds.

Sulfur-containing compounds are essential motifs of natural molecules. We herein report a photoinduced iron-catalyzed strategy for efficient sulfoxide deoxygenation under mild conditions. The iron catalyst as the sole additive acts dually: it activates hydrocarbon reductants (also as a solvent) via a ligand-to-metal charge transfer pathway and serves as an "electron buffer" to regulate subsequent electron transfer. This unique mechanism enables a non-chromatography protocol with high efficiency (majority at >95%, up to 99%) and selectivity. The operationally simple method exhibits broad functional group tolerance and wide application in late-stage transformation of drug-derived sulfoxides into bioactive sulfides.

Indoles are privileged structural motifs in N-heterocyclic chemistry, while developing a general and facile platform capable of directly transforming commodity chemicals into multi-functionalized indoles persists as an unmet challenge. Herein, we present a photo-driven bifunctional iron-catalyzed strategy for one-pot synthesis of indoles from readily available arylamines and alkanes/carboxylic acids. By leveraging a synergistic combination of iron-based photocatalysis via ligand-to-metal charge transfer pathway and Lewis acid catalysis, the method enables efficient C(sp³)–H activation or decarboxylation followed by sigmatropic rearrangement cyclization under mild conditions. The protocol demonstrates broad substrate scope (152 examples), excellent functional group tolerance, and high yields (up to 95%), facilitating the direct construction of diverse indole scaffolds without pre-functionalization. Notably, the methodology can be successfully applied to the concise and scale-up total synthesis of several pharmacologically relevant indole derivatives, including Iprindole, Mebhydrolin, Melatonin, and A-FABP inhibitor, underscoring its practicality and potential for industrial application in pharmaceutical manufacturing.

Microscale high-throughput screening enables a mild Cu/photoredox benzylic C(sp ³ )–C(sp ² ) Suzuki–Miyaura coupling. Quantitative modeling distinguishes visually apparent trends from reproducible predictive relationships.

This study introduces a photoinduced Suzuki-Miyaura C(sp²)-C(sp³) coupling protocol in which the introduction of a nitrene reagent efficiently redirects the conventional C(sp²)-C(sp³) linkage toward a C(sp²)-N-C(sp³)-bridged architecture. A total of 432 reactions were conducted using a high-throughput screening strategy to identify the optimal parameters. This strategy exhibits mild conditions, convenient operation, and good functional group tolerance, meanwhile establishing a solid foundation for further developing novel catalytic systems of cross-coupling reactions.

Differentially substituted phosphines are indispensable in medicines, materials, and catalysis, yet their customizable synthesis, traditionally depending on unstable P─H/halogen reagents, remains formidably challenging. Here, we report a photoredox strategy enabling controllable aryl substitution through chemoselective P─C cleavage. By engineering electron donor‐acceptor complexes between phosphonium salts and tertiary amines, this metal‐free protocol realizes three consecutive hydrocarbyl exchanges for delivering tri‐diverse‐aryl phosphines with transition metal contamination elimination and broad functional group tolerance including unprotected amines and hydroxyls, facilitating late‐stage modification of drugs/commercial ligands and construction of P,O,S‐tridentate architectures and chiral P‐stereogenic centers. Mechanistic studies reveal the dynamic pentacoordinated‐phosphorane‐complex formation nature and the radical‐intermediate pathway, while the chemoselectivity originates from different P─C bond strengths. This work establishes a modular and sustainable platform for programming‐level precision phosphine engineering.

Differentially substituted phosphines are indispensable in medicines, materials, and catalysis, yet their customizable synthesis, traditionally depending on unstable P─H/halogen reagents, remains formidably challenging. Here, we report a photoredox strategy enabling controllable aryl substitution through chemoselective P─C cleavage. By engineering electron donor‐acceptor complexes between phosphonium salts and tertiary amines, this metal‐free protocol realizes three consecutive hydrocarbyl exchanges for delivering tri‐diverse‐aryl phosphines with transition metal contamination elimination and broad functional group tolerance including unprotected amines and hydroxyls, facilitating late‐stage modification of drugs/commercial ligands and construction of P,O,S‐tridentate architectures and chiral P‐stereogenic centers. Mechanistic studies reveal the dynamic pentacoordinated‐phosphorane‐complex formation nature and the radical‐intermediate pathway, while the chemoselectivity originates from different P─C bond strengths. This work establishes a modular and sustainable platform for programming‐level precision phosphine engineering.