Science China Chemistry最新文献

Development of efficient and versatile methods for functional group transformations is one major objective in modern organic synthetic chemistry. α-Ketophosphonates are a class of bifunctional compounds playing a prominent role in organic and medicinal chemistry. However, their broader applicability has been hampered by lacking of direct and convenient synthetic methods from stable and abundant starting materials. Direct transformation of readily available and robust amides into labile α-ketophosphonates is thus highly desirable but remains a formidable challenge, as such a reaction is both kinetically and thermo-dynamically unfavorable, and there exists a chemoselective issue for the known bisphosphonylation. Herein, we report unprecedented versatile synthesis of α-ketophosphonates, α-hydroxyphosphonates and α,α-difluorophosphonates from either secondary or tertiary amides. The reactions are enabled by in situ electrophilic activation with trifluoromethanesulfonic anhydride (Tf₂O). The method features high efficiency, good chemoselectivity, wide substrate scope, excellent functional group tolerance, and easy scalability. The practicality of this methodology is highlighted by the late-stage functionalization of drug molecules and concise formal synthesis of an FBPase inhibitor.

The oxide-zeolite (OXZEO) bifunctional catalysts have gained significant attention as an effective strategy to address the selectivity challenges in direct syngas conversion beyond Fischer-Tropsch synthesis (FTS). In OXZEO catalysis, the metal oxide component is mainly responsible for activating CO and H₂, therefore determining the overall activity and product selectivity. Recent advances in sophisticated in-situ and quasi-in situ characterization techniques have shed light on the active sites of metal oxides and CO activation and its hydrogenation mechanism. This review focuses on these fundamental understandings, discussing the challenges and future directions.

Proteolysis-targeting chimeras (PROTACs) achieve therapeutic effects by degrading disease-related proteins but face limitations due to off-target toxicity caused by poor spatial control. To address this, we developed a near-infrared (NIR)-activated photocaged PROTAC platform that enables precise molecular spatiotemporal control over protein degradation. Two degraders targeting oncology-relevant proteins, breakpoint cluster region gene-abelson gene (BCR-ABL) and bromodomain-containing protein 4 (BRD4), showed light-dependent activation. NIR irradiation induced efficient target degradation (>70%) in cancer models, considerably improving therapeutic outcomes and reducing metastatic behavior. In animal studies, NIR-activated degraders demonstrated strong tumor suppression without detectable toxicity, outperforming light-restricted controls. Overall, this platform provides spatiotemporally controlled protein degradation with enhanced tissue penetration, offering a promising approach to reduce off-target effects in precision oncology.

Chirality is a fundamental geometric property that manifests across molecular and nanoscale systems, profoundly influencing physical, chemical, and biological processes. At the intersection of chiral chemistry and nanoscience, chiral nanomaterials have emerged as a transformative class of materials, exhibiting unique spin-dependent properties governed by the chiral-induced spin selectivity (CISS) effect. This quantum phenomenon, rooted in spin-orbit coupling and spin filtering mechanisms, enables precise modulation of electron spin polarization, unlocking new opportunities in catalysis, spintronics, and energy conversion. This review provides a comprehensive overview of the CISS effect in chiral nanomaterials, elucidating its underlying mechanisms—including spin-orbit interactions, spin filtering, and spin blockade—and surveying advanced techniques for characterizing both structural chirality and spin polarization. We further highlight emerging applications in electrocatalysis, photocatalysis, and spintronic device engineering. Despite significant progress, key challenges remain in unraveling the fundamental physics, achieving accurate spin characterization, and translating these phenomena into robust, scalable technologies. Continued interdisciplinary research into the rational design and functionalization of chiral nanomaterials is poised to drive breakthroughs in sustainable energy, next-generation catalysis, and quantum information technologies.