Xuemei Zhang

Alkene hydrogenation reactions are essential processes widely utilized across diverse scientific fields for the production of pharmaceuticals, natural products, and various functional materials. Current strategies (e.g., metal hydrogen atom transfer [mHAT], photo/electrochemistry) consistently necessitate compromises, invariably involving transition metals, pressurized H ₂ , or solvent‐intensive conditions. Herein, we report a mechanochemical hydrogenation reaction of both activated and unactivated alkenes via piezoelectric catalysis under conditions that are free from transition‐metals, H ₂ gas, and solvents. This approach exhibits good compatibility with various functional groups and demonstrates a broad substrate scope. In addition, the hydrogenation of bioactive molecule derivatives for modification purposes highlights its potential applications in the pharmaceutical industry. Based on mechanistic investigations, we propose a potential mechanism for the alkene hydrogenation via piezoelectric catalysis.

A mechanochemical, base-catalyzed strategy achieves rapid, metal-free isomerization and deuteration of allylbenzenes, enabling precise CD ₃ incorporation under ambient conditions within 15 minutes.

Radical‐mediated selenylation has emerged as a powerful strategy for constructing carbon‐selenium bonds. While effective for generating aryl selenyl radicals, current approaches for producing alkyl selenyl radicals remain underdeveloped. In this study, we present a mechanochemical approach that enables the modular generation of alkyl selenyl radicals from elemental selenium and alkyl halides, thereby advancing the hydroselenation of alkenes. The modular generation of alkyl selenyl radicals utilizes abundant and commercially available alkyl (pseudo)halides as radical precursors, activated through mechanical force to overcome selenium's inherent inertness. The reaction proceeds under ambient conditions with minimal solvent usage, achieving a broad substrate scope encompassing alkyl iodides, bromides, chlorides, and sulfonates. Notably, mechanistic experiments and density functional theory (DFT) calculations indicate that both PhSiH ₃ or/and H ₂ O can function as hydrogen atom donors through a radical pathway. This finding appears to be significant in the case of water, where the oxophilicity of silicon likely provides the driving force, pointing to a plausible silicon‐mediated activation of water. We therefore propose a mechanochemical silicon‐mediated radical process where coordination‐induced bond weakening could enable intermolecular hydrogen atom transfer (HAT) from H ₂ O to carbon radicals.

Deuterium labeling is extensively utilized across various scientific disciplines. The dehalogenative deuteration of organic halides offers a promising approach for achieving deuterium labeling. However, existing methods for dehalogenative deuteration primarily focus on sp ² ‐hybridized aryl halides, while sp ³ ‐hybridized alkyl halides, especially bromides and chlorides, exhibit low reactivity and pose significant challenges for reduction. This limitation hampers the development of deuteration methodologies. In this study, a robust and versatile mechanochemical strategy is introduced for deuterating both activated and unactivated alkyl halides (X = Cl, Br, I), employing D ₂ O as an economical deuterium source and electron donor, catalyzed by a piezoelectric material. Importantly, unlike previously mechanochemical piezoelectric catalysis reactions that are typically initiated by a single‐electron reduction process, this transformation is triggered by a single‐electron oxidation pathway. Employing this innovative technique, a variety of organic halides are successfully converted, including primary, secondary, and tertiary alkyl halides, into deuterated products with good yields and high deuterium incorporation, using only a chemically equivalent amount of D ₂ O. The practical application of this green and efficient methodology is further demonstrated by late‐stage deuteration on drug molecule analogs, underscoring its potential utility in pharmaceutical development.

Unsymmetric disulfides are prevalent in natural products and are essential in medicinal chemistry and materials science, but their robust synthesis poses significant challenges. In this paper, we report an expeditous transition-metal-free methodology for synthesizing unsymmetric disulfides through the addition of perthiyl radicals to alkenes. This study marks the use of generating perthiyl radicals by reacting SO₂ with unactivated alkyl (pseudo)halides (Cl/Br/I/OTs). Various primary, secondary and tertiary alkyl (pseudo)halides substituted with different functional groups successfully function as suitable reactants. The formation of perthiyl radicals and their involvement in the reaction process are verified through mechanistic studies and DFT calculations. Overall, this method leverages readily available alkyl electrophiles and alkenes alongside SO₂ in a single reaction setup to efficiently form both carbon-sulfur and sulfur-sulfur bonds simultaneously.

We present a novel palladium-catalyzed asymmetric Tsuji–Trost reaction featuring sulfur dioxide insertion through a palladium-sulfonyl intermediate. This method yields α-chiral sulfonates with high efficiency and excellent enantioselectivities.

β-Amino sulfones find extensive applications in pharmaceuticals, natural products, agrochemicals, and organic synthesis. Meanwhile, aziridine units are recognized as valuable intermediates in contemporary synthetic chemistry for efficient synthesis of β-functionalized amines through ring-opening reactions. However, the ring-opening sulfonylation of aziridines via SO₂ insertion, granting access to β-amino sulfones, remains unexplored. In this paper, we present a novel transition-metal-catalyzed system for the first regiodivergent sulfonylation of aziridines using SO₂ insertion to produce β-amino sulfones successfully. This method is distinguished by its mild reaction conditions, a broad substrate scope, ease of execution, and exceptional regioselectivity.

The Reppe sulfonylation reaction has remained substantially underexplored. We present a novel method for Reppe sulfonylation involving SO₂ insertion, remarkably without the need for metal catalysts, instead utilizing Brønsted bases as catalysts.

A copper-catalyzed three-component sulfonation reaction utilizing enol silyl ether, N-acyloxyamine, and sulfur dioxide is introduced. This method provides a convenient and straightforward pathway to synthesize a variety of structurally diverse β-keto sulfonamides with satisfactory yields under mild reaction conditions. The protocol exhibits broad substrate compatibility and demonstrates good tolerance towards a variety of functional groups. Additionally, the successful execution of this reaction on a gram scale and the demonstration of several transformations with β-keto sulfonamides underscore the method's practical applicability. Preliminary mechanistic studies suggest that this transformation may involve a radical process.