Xiangyang Chen

In this study, we have discovered a previously neglected interface modification mechanism. Specifically, isolated olefin moieties are capable of donating π‐electrons to metal surfaces, which in turn generates an interfacial dipole and leads to a substantial reduction in the electrode work function. This strategy demonstrates broad applicability across a range of olefin‐containing molecules. Through comparative studies on various metals, it has been determined that silver (Ag) exhibits the most pronounced π→metal donation interaction. When olefin‐functionalized materials are employed as the cathode interlayer (CIL) in organic solar cells (OSCs), they can enhance the built‐in electric field, promote the formation of ohmic contact, improve charge extraction efficiency, and suppress trap‐assisted recombination, resulting in a power conversion efficiency (PCE) of 20.88% with a high fill factor over 83% in D18:L8‐BO system. Further analysis by depth‐profile x‐ray photoelectron spectroscopy (XPS) reveals a significant suppression of Ag migration, highlighting the ability of olefin CILs to enhance device stability. Our research indicates that olefins represent a novel class of electrode‐modifying groups with stable chemical properties and electron‐donating characteristics, offering promising prospects for the development of high‐performance, long‐lifetime organic photovoltaic cell technologies.

In this study, we have discovered a previously neglected interface modification mechanism. Specifically, isolated olefin moieties are capable of donating π‐electrons to metal surfaces, which in turn generates an interfacial dipole and leads to a substantial reduction in the electrode work function. This strategy demonstrates broad applicability across a range of olefin‐containing molecules. Through comparative studies on various metals, it has been determined that silver (Ag) exhibits the most pronounced π→metal donation interaction. When olefin‐functionalized materials are employed as the cathode interlayer (CIL) in organic solar cells (OSCs), they can enhance the built‐in electric field, promote the formation of ohmic contact, improve charge extraction efficiency, and suppress trap‐assisted recombination, resulting in a power conversion efficiency (PCE) of 20.88% with a high fill factor over 83% in D18:L8‐BO system. Further analysis by depth‐profile x‐ray photoelectron spectroscopy (XPS) reveals a significant suppression of Ag migration, highlighting the ability of olefin CILs to enhance device stability. Our research indicates that olefins represent a novel class of electrode‐modifying groups with stable chemical properties and electron‐donating characteristics, offering promising prospects for the development of high‐performance, long‐lifetime organic photovoltaic cell technologies.

Asymmetric catalysis enabled by dinucleating ligands remains markedly underdeveloped compared with the mature field of mononuclear asymmetric catalysis. Here, we report the development of a modular chiral dinucleating ligand based on a 6-phosphinylpyridine-oxazoline skeleton, which can undergo self-assembly upon coordination to form dinuclear complexes with a sterically confined chiral pocket. The catalytic capability and unique chiral environment of this ligand were evaluated by successfully applying it in two types of asymmetric dearomative propargylations, including a stereodivergent synthesis of spiroindolenines bearing two stereocenters. The diverse transformations of the chiral spirocyclic products, including the preparation of chiral dihydroanthracenes via rearrangement, established a versatile platform for accessing valuable molecular scaffolds. Furthermore, mechanistic investigations indicated that dinuclear species are involved in the catalytic cycle, with insights into the enantio-determining steps and the key orbital interaction in the dicopper-allenylidene intermediate.

Although transition metal–catalyzed C─H activation has notably advanced C─H functionalization, achieving highly selective C─H difunctionalization remains a substantial challenge. Current C─H difunctionalization strategies remain largely constrained to two-component annulation reactions or dicarbofunctionalization, which inherently limit structural diversity and synthetic efficiency. Here, we report a palladium-catalyzed three-component C─H 1,3- N , O -difunctionalization of 3-phenylpropanamide using azodicarboxylate in conjunction with either dioxygen or carboxylic acid. This approach selectively delivers distinct 1,3- N , O -difunctionalized products through either photothermal or thermal pathway, affording moderate to high yields with excellent site selectivity and broad functional group tolerance, which can be readily transformed into various valuable heterocyclic compounds. Extensive experimental and computational studies reveal that the reaction operates via a complex and continuous catalytic cycle rather than by tandem, independent steps. By integrating principles of C─H activation, electrophilic amination, difunctionalization, and photothermal catalysis, this work expands the toolbox for selective multiple bond formation and will attract more interest in various fields.

We report the first example of an uncyclized cis -selective dearomatization reaction using a radical docking-migration strategy. The reaction proceeds readily under photochemical conditions without the use of extra photosensitizers.

Recent advancements in synthetic chemistry have sparked significant interest in bridged compounds, particularly azabicyclo[x,1,1]alkanes (ABCAs), which have emerged as critical structural motifs in medicinal chemistry. These compounds are highly valued for their unique geometric constraints, enhanced target selectivity, and favorable pharmacokinetic profiles, making them valuable tools in drug discovery. However, despite their importance, the construction of diverse ABCA motifs remains a significant challenge, as existing methodologies are often limited to specific ring systems and substituents. In this study, we present a modular synthetic strategy for the construction of ABCA motifs. The key of this approach lies in the successful synthesis of a series of highly strained azatricycloalkanes, such as 1-azatricyclo[4.1.0.0²,⁷]heptane. By leveraging stereocontrolled transformations of the strained C–N bonds within these azatricycloalkanes, we have synthesized a wide range of ABCA derivatives with unprecedented structural diversity. This methodology has been effectively utilized in the development of novel orexin receptor antagonists and bioisosteres, showcasing its potential to advance drug discovery for therapeutic applications.

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration of cyclopropenes, with less reactive alkyl iodides as electrophiles, for the efficient synthesis of tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, a broad substrate scope, and good functional group tolerance, affording an array of chiral borylated cyclopropanes in good to high yields with excellent diastereo- and enantioselectivities. Detailed mechanistic experiments and kinetic studies were conducted to elucidate the reaction pathway and the rate-determining step of the reaction. DFT calculations revealed that the π···π stacking interaction between the phenyl groups on the substrate and the phosphorus ligand, along with the smaller distortion in the CuL-Bpin part, contributed to the high diastereo- and enantioselectivities. The synthetic utility of the protocol was showcased by the facile synthesis of some valuable chiral cyclopropanes with multiple chiral centers.