Pierre Plouard, Laura Borrel, Pierre-Olivier Butin, Paul Muller, Rémi Cherpitel, Séverine Loiseau, Ludovic Clarion, David Virieux, Tahar Ayad
{"title":"Ru-Catalyzed Asymmetric Transfer Hydrogenation of α-iminophosphonates: A Novel Synthetic Approach for Valuable Chiral α-Aminophosphonates.","authors":"Pierre Plouard, Laura Borrel, Pierre-Olivier Butin, Paul Muller, Rémi Cherpitel, Séverine Loiseau, Ludovic Clarion, David Virieux, Tahar Ayad","doi":"10.1002/chem.202502405","DOIUrl":"https://doi.org/10.1002/chem.202502405","url":null,"abstract":"<p><p>A novel Ru-catalyzed asymmetric transfer hydrogenation (ATH) strategy has been developed for the efficient synthesis of valuable chiral α-aminophosphonates from readily available α-iminophosphonates. This method enables the conversion of both acyclic and cyclic substrates in high yields (up to 97%) and excellent enantioselectivities (up to >99:1), providing a practical entry to phosphorus-containing chiral amines. Notably, this is the first reported application of ATH to α-iminophosphonates, offering a robust and operationally convenient alternative to conventional asymmetric hydrogenation (AH) approaches.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02405"},"PeriodicalIF":3.7,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Cyclization Enhances Luminescence Efficiency of a Fluorescent Probe for Amyloid-β in Alzheimer's Disease.","authors":"Xiaomeng Sun, Wenshuo Chen, Tian Shi, Jie Sun, Wei Hu, Yujin Zhang","doi":"10.1002/chem.202502134","DOIUrl":"https://doi.org/10.1002/chem.202502134","url":null,"abstract":"<p><p>Alzheimer's disease (AD) is a neurodegenerative disease characterized by β-amyloid (Aβ) deposition, imposing significant social and economic burdens globally. Despite extensive efforts have been devoted to developing fluorescent probes for Aβ imaging, further improving the luminescent efficiency of prevailing probes still remains a significant challenge. Herein, we investigated the inner mechanism of constructing high-efficient Aβ probes via a structural cyclization strategy. Based on a typical donor-acceptor Aβ probe (Pro1), three cyclized derivatives (Pro2-Pro4) are designed by incorporating dimethylene, trimethylene, and ethyleneoxy groups into the π-conjugated bridge. It is found that all compounds exhibit high specificity at various binding sites within the Aβ fibril, while Pro4 features preferable hydrogen bond interaction with the fibril. Notably, a significant enhanced fluorescence quantum efficiency is demonstrated in the ethyleneoxy-contained counterpart, primarily due to the decreased nonradiative decay arising from the reduced nonadiabatic electronic coupling, electron-vibration coupling, and vibrational modes mixing. Consequently, the newly designed compound Pro4 achieves both red-shifted emission and optimal luminescent efficiency, making it a promising candidate for Aβ imaging. These findings highlight the feasibility of structural cyclization as an effective approach to improve luminescent efficiency in Aβ-targeted probes, contributing to the development of fluorescent imaging techniques for early AD diagnosis.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02134"},"PeriodicalIF":3.7,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gustavo T Feliciano, Kalishankar Bhattacharyya, Alexander A Auer
{"title":"Direct and Indirect Effects of Fe-Incorporation in Nickel(oxy)hydroxide Materials for the Electrocatalytic Oxygen Evolution Reaction - Employing Constant pH/U Models for Deeper Insights.","authors":"Gustavo T Feliciano, Kalishankar Bhattacharyya, Alexander A Auer","doi":"10.1002/chem.202501441","DOIUrl":"https://doi.org/10.1002/chem.202501441","url":null,"abstract":"<p><p>In this study, we seek to deepen the understanding of the Fe effect in Ni-oxyhydroxide-mediated oxygen evolution reaction (OER) electrocatalysis in alkaline conditions, where extremely small amounts of Fe can have a dramatic impact on catalytic performance. For this purpose, Density Functional Theory (DFT) electronic structure calculations with implicit solvation description is employed in a constant pH/potential simulation framework. Nanoparticle models are considered for the nickel-based oxyhydroxide material with different degrees of Fe incorporation, and the pH/U-dependent interface structure is studied. It can be seen that Fe incorporation influences the total extent of oxidation and deprotonation, stabilizing oxo species at early states of the reaction even at lower potentials. From the resting state models, we derive reaction energy profiles and O-O coupling barriers for three different OER mechanisms: water nucleophilic attack (WNA), intramolecular coupling (IMC), and the lattice oxygen mechanism (LOM). Each species is derived taking into account explicit change in protonation state and charge as a function of pH and potential. The results suggest direct and indirect modifications in Ni-oxyhydroxide reactivity and in the preferred OER pathway, which changes with Ni/Fe ratio. The results we present imply that synergy between Ni and Fe acid-base and redox properties is essential for efficient water oxidation/deprotonation and O-O bond formation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01441"},"PeriodicalIF":3.7,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Advancement in Boron-Embedded Amino Acids: Enhancing Boron Neutron Capture Therapy for Improved Cancer Treatment Efficacy.","authors":"Saira Qurban, Hao-Wen Jiang, Peng-Fei Xu","doi":"10.1002/chem.202501961","DOIUrl":"https://doi.org/10.1002/chem.202501961","url":null,"abstract":"<p><p>One of the most difficult issues facing humanity today is the treatment of cancer. A binary cancer treatment called boron neutron capture therapy (BNCT) works especially well for high-grade gliomas and metastatic brain malignancies. Due to their preferential absorption by developing tumor cells, boronated amino acids have drawn a lot of attention among the several boron-containing compounds utilized as BNCT agents. In the first section of this review, the fundamental ideas of BNCT are briefly presented. In the remaining sections, we present a thorough analysis and synthesis of several boronated amino acids using distinct techniques. This article summarizes the therapeutic prospects of boron delivery agents and offers a critical analysis of them from the perspectives of nuclear medicine doctors and medicinal chemists.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01961"},"PeriodicalIF":3.7,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Regioselective Ring-Opening Polymerization of Asymmetric Cyclic Dimers for Polyester-Based Alternating Copolymers.","authors":"Weijie Qiu, Xiaoyan Tang","doi":"10.1002/chem.202502142","DOIUrl":"https://doi.org/10.1002/chem.202502142","url":null,"abstract":"<p><p>Sequence-controlled polyester-based alternating copolymers have attracted significant interest due to their biocompatibility, biodegradability, closed-loop recyclability, and hydrolytic degradability, offering broad potential in biomedical and sustainable materials. Among the available strategies, regioselective ring-opening polymerization (ROP) of asymmetric cyclic di(thio)esters and cyclic(ester-amide)s has emerged as a promising approach for constructing alternating copolymers with precise sequence- and stereo-control, structural diversity, and tunable properties. This review classifies asymmetric cyclic monomers into two categories: (1) monomers with two aliphatic ester bonds, where regioselectivity is mainly dictated by steric differences and typically requires tailored metal catalysts; and (2) monomers with chemically distinct reactive sites (e.g., phenolic ester, thioester, or amide vs. aliphatic ester), which enable near-perfect regioselectivity using simple catalysts. Recent progress in the synthesis of alternating aliphatic copolyesters, poly(phenolic-alt-aliphatic ester)s, poly(ester-alt-thioester)s, and poly(ester-alt-amide)s is highlighted, emphasizing their enhanced degradability, recyclability, and mechanical performance. Key advances in catalyst optimization, mechanistic understanding, quantification of regioselectivity, and the structure-property relationships of alternating copolymers are summarized. Finally, future directions are discussed, including rational catalyst design, expansion to new monomer architectures, and the systematic evaluation of how regioselectivity governs alternating copolymer properties.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02142"},"PeriodicalIF":3.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022450","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Weiqing Xu, Linyu Zeng, Jiarong Nan, Weiran Ling, Hai Xiong
{"title":"Fe<sup>3+</sup> and H<sup>+</sup>-triggered \"Turn-on\" Fluorescence Probe Based on Lysosomal-targeted RBH-EdC for Monitoring Intragastric Acidity.","authors":"Weiqing Xu, Linyu Zeng, Jiarong Nan, Weiran Ling, Hai Xiong","doi":"10.1002/chem.202501717","DOIUrl":"https://doi.org/10.1002/chem.202501717","url":null,"abstract":"<p><p>The long-term visualization of intracellular Fe<sup>3+</sup> dynamics and lysosomal activity is crucial for investigating the physiological roles and functions of lysosomes during the growth of organisms. The lysosome-targeted fluorescent probe (RBH-EdC), derived from rhodamine-nucleoside conjugates, demonstrates a sophisticated dual-activation design: one is Fe<sup>3</sup>⁺ response, triggering spirolactam ring-opening to form xanthine structures, resulting in ≥ 1000-fold fluorescence enhancement with visible colorimetric transition (colorless→pink). Another is pH sensitivity, demonstrating protonation-dependent fluorescence amplification at the dC at site N3 (pK<sub>a </sub>= 2.9), achieving a 30-fold intensity increase at pH 2.5 within the 1.0-5.0 range. Remarkably, the RBH-EdC/Fe<sup>3</sup>⁺ complex showed a further significant 20-fold fluorescence enhancement at pH 3.0. This Fe<sup>3</sup>⁺/H⁺ co-activated \"turn-on\" system provides exceptional signal amplification for both in vitro and in vivo applications, enabling precise exploration of lysosome-related biological processes, including the response of the pH microenvironment, real-time monitoring of lysosomal pH dynamics, in situ measurement of gastric acidity levels, and potential application in gastric ulcer diagnostics.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01717"},"PeriodicalIF":3.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022504","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dion B Nemez, Robert J Ortiz, Keighlynn A Veilleux, J A Gareth Williams, David E Herbert
{"title":"In Pursuit of Low Energy Phosphorescence: Late Metal Coordination Complexes of the Planar, π-extended Bipyridyl Ligand 6,6',7,7'-Biphenanthridine.","authors":"Dion B Nemez, Robert J Ortiz, Keighlynn A Veilleux, J A Gareth Williams, David E Herbert","doi":"10.1002/chem.202501802","DOIUrl":"https://doi.org/10.1002/chem.202501802","url":null,"abstract":"<p><p>The coordination chemistry of the planar, doubly π-extended bipyridine analog, 6,6',7,7'-biphenanthridine (p-biphe), is presented. The phenanthridine units in p-biphe are fused together at the 6- and 7- positions, and the resulting rigid ligand is compared with the more flexible parent \"biphe\" fused only at the 6-positions. p-Biphe is intensely fluorescent in solution with a much higher quantum yield, but, unlike biphe, at 77 K the fluorescence is not accompanied by any significant phosphorescence. Two four-coordinate Cu(I) complexes and pseudo-octahedral Ru(II) and Ir(III) complexes are described: [Cu(p-biphe)<sub>2</sub>]<sup>+</sup>, [(P^P)Cu(p-biphe)]<sup>+</sup>, [Ru(bpy)<sub>2</sub>(p-biphe)]<sup>2+</sup>, and [Ir(ppy)<sub>2</sub>(p-biphe)]<sup>+</sup>, isolated as PF<sub>6</sub> salts (P^P = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine). The complexes are strongly coloured due to intense low-energy absorption to charge-transfer excited states based on TDDFT calculations. The acceptor nature of the p-biphe ligand is clear from multiple reduction events observed electrochemically. The Ir(III) complex displays remarkably low-energy phosphorescence (λ<sub>max</sub> = 812 nm) in solution at room temperature with a vibrational progression evident extending into the near IR, with no contamination from visible light emission. While the heteroleptic Cu(I) complex is phosphorescent at 77 K, no emission is detectable from [Cu(p-biphe)<sub>2</sub>]<sup>+</sup> or [Ru(bpy)<sub>2</sub>(p-biphe)]<sup>2+</sup>, likely due to competitive nonradiative decay.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e01802"},"PeriodicalIF":3.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Coronene Bisimide as a Visible-Light-Mediated Triplet-Triplet Energy Transfer Catalyst.","authors":"Divya P Sukumaran, Frank Würthner","doi":"10.1002/chem.202502602","DOIUrl":"https://doi.org/10.1002/chem.202502602","url":null,"abstract":"<p><p>Photosensitization has emerged as a versatile tool to facilitate access to excited states under mild conditions, allowing for efficient and selective photochemical transformations. Herein, we report a very simple molecule, coronene bisimide (CBI), as a potent visible-light photosensitizer featuring a high extinction coefficient with a broadband absorption spanning from ultraviolet to green region of the visible spectrum, along with a long-lived triplet state generated via efficient intersystem crossing (ISC). Utilizing the triplet-triplet energy transfer (TTEnT) strategy, CBI catalyzes diverse reactions under green light irradiation. Through this, we propose CBIs as a new class of heavy-atom-free visible-light sensitizers overcoming the limitations of conventional sensitizers, such as low extinction coefficient in the visible regime, short triplet-state lifetimes, and high toxicity, by relying on heavy atoms.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02602"},"PeriodicalIF":3.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Glycosyl Radical-Based, 1,2-trans-Selective Synthesis of C-Aryl Glycosides from Glycals Enabled by Photoredox PCET/Nickel-Dual Catalysis.","authors":"Hui Zeng, Wei Ouyang, Shuai Liu, Jing Wang, Pei-Xin Rui, Xiang-Guo Hu","doi":"10.1002/chem.202502233","DOIUrl":"https://doi.org/10.1002/chem.202502233","url":null,"abstract":"<p><p>We report a glycosyl radical-based, 1,2-trans-selective synthesis of C-aryl glycosides of 2-deoxy-2-amino-sugars from glycals via photoredox PCET/Ni dual catalysis. Mechanistic studies indicate that glycosyl radical formation involves the generation of an N-radical through a proton-coupled electron transfer (PCET) process, followed by its addition to the glycal. This protocol features: a) the use of an inexpensive organic photosensitizer and readily available glycals and aryl bromides; b) good functional group tolerance for both aryl bromides and glycal substrates; c) excellent diastereoselectivity, with exclusive formation of the 1,2-trans C-glycosides in all cases. Furthermore, the reaction could be conducted on gram-scale and is suitable for the late-stage modification of complex molecule. Deprotection experiments demonstrated complementary stability profiles between the oxazolidinone protecting group employed here and the dihydrooxazole group in our previous work.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02233"},"PeriodicalIF":3.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A Phosphorus(V)-Centered Porphyrin Having Redox- and Air-Stable Axial P-H Bonds.","authors":"Shintaro Ishida, Yoshiki Ota, Nozomu Kuwabara, Takuroh Hatakeyama, Takeaki Iwamoto","doi":"10.1002/chem.202502215","DOIUrl":"https://doi.org/10.1002/chem.202502215","url":null,"abstract":"<p><p>Phosphorus(V)-centered porphyrins (P(V)-porphyrins) are an important class of functional dyes in many fields of research, and axial ligands on the phosphorus atom affect the electronic properties of P(V)-porphyrins and add functions. Herein, we report on the synthesis and characterization of a hitherto unknown P(V)-porphyrin having hydrogen atoms as axial ligands (1<sup>+</sup>·PF<sub>6</sub> <sup>-</sup>, PF<sub>6</sub> <sup>-</sup> is a counter anion). Synthesis of 1<sup>+</sup>·PF<sub>6</sub> <sup>-</sup> was achieved by treatment of dichloro-derivative (2<sup>+</sup>·Cl<sup>-</sup>) with LiAlH<sub>4</sub> followed by AgPF<sub>6</sub> via hydride reduction accompanied by one-electron reduction and one-electron oxidation. The porphyrin core of 1<sup>+</sup>·PF<sub>6</sub> <sup>-</sup> is nonplanar but considerably ruffled. The cyclic voltammogram of 1<sup>+</sup>·PF<sub>6</sub> <sup>-</sup> exhibits two reversible waves, which indicates redox couples among 1<sup>+</sup>, neutral radical 1<sup>•</sup>, and 1<sup>-</sup>. Compound 1<sup>+</sup>·PF<sub>6</sub> <sup>-</sup> is tolerant toward air despite its PH<sub>2</sub> moiety due to the energetically low-lying HOMO (highest occupied molecular orbital) and σ(P-H) orbitals.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02215"},"PeriodicalIF":3.7,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145008100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}