Angewandte Chemie最新文献

{"title":"Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers","authors":"Alejandro Rey,&nbsp;Dr. Andrés Arribas,&nbsp;Prof. Dr. José L. Mascareñas,&nbsp;Dr. Fernando López","doi":"10.1002/ange.202512027","DOIUrl":"https://doi.org/10.1002/ange.202512027","url":null,"abstract":"<p>An iridium complex featuring the perfluorinated bisphosphine ligand d^Fppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using <i>N</i>-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202512027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrophilic Iridium Bis-N-Heterocyclic Carbene Complexes Catalyze Linear-Selective, Additive-Free Hydroaminomethylation of Long-Chain Olefins in Water","authors":"Yinghao Huo,&nbsp;Xinyi Zhou,&nbsp;Guanfeng Liang,&nbsp;Dr. Xin He,&nbsp;Dr. Qingshu Zheng,&nbsp;Prof.Dr. Tao Tu","doi":"10.1002/ange.202508793","DOIUrl":"https://doi.org/10.1002/ange.202508793","url":null,"abstract":"<p>Aqueous hydroaminomethylation (HAM) of olefins generally requires the use of organic solvents, additives, and high-pressure hydrogen to synthesize amines in satisfactory yields and selectivity. Herein, we accomplish the HAM reactions of long-chain olefins in water without organic solvent or additives by using a hydrophilic bis-NHC-Ir complex as the catalyst. A broad scope of long-chain olefins and amines is well compatible, affording corresponding higher amines in up to 99% yields with excellent linear/branched (<i>l/b</i>) selectivity (up to 94/6). Mechanistic investigations reveal that water acts as both solvent and hydrogen source. The protocol can be readily extended to the synthesis of pharmaceuticals and deuterated analogues with excellent yields and deuterium rates. Moreover, the amine products are easily separated by extraction, and the recovered aqueous phase could be directly used and recycled. This protocol offers a sustainable, safe, and cost-effective approach for synthesizing higher amines.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cyclochlorotine Hydroxylase CctR Reveals DUF3328 as a Family of Copper-Dependent Metalloenzymes","authors":"Wentao Huang,&nbsp;Jakob K. Reinhardt,&nbsp;Anru Tian,&nbsp;Xiao Zhang,&nbsp;Binghui Li,&nbsp;Noah Gould,&nbsp;Sashirekha Nallapati,&nbsp;Alexander R. Ivanov,&nbsp;Yi Wang,&nbsp;Jason J. Guo,&nbsp;David E. Budil,&nbsp;Jing-Ke Weng","doi":"10.1002/ange.202512449","DOIUrl":"https://doi.org/10.1002/ange.202512449","url":null,"abstract":"<p>DUF3328 is a protein family widely found in fungal natural product biosynthesis pathways. Although DUF3328 proteins have long been implicated in diverse modifications of inert C(<i>sp³</i>)─H bonds, including halogenation, hydroxylation, and macrocyclization, the biochemical properties and catalytic mechanisms of DUF3328 proteins remain elusive. Here, we report the characterization of the DUF3328 protein CctR, which catalyzes C(<i>sp³</i>)─H hydroxylation of fungal cyclic peptide cyclochlorotine. Through AlphaFold modeling, in vitro biochemical characterization, and spectroscopic analysis, we demonstrate that CctR is a membrane-associated copper-dependent enzyme that functions as a homodimer. The dimerization of CctR is mediated by its transmembrane helix, a four-helix coiled coil, and C-terminal disulfide bonds. The conserved HxxHC(x)_nHxxHC motif, characteristic of the DUF3328 superfamily, is anchored on the dimerization interface and forms a binuclear copper coordination center. Moreover, we show that CctR is dioxygen-dependent and requires electron input for the hydroxylation reaction. Together, these findings define DUF3328 as a previously unrecognized family of binuclear copper-dependent metalloenzymes, capable of catalyzing diverse chemical transformations, and lay the groundwork for future discovery of novel biocatalysts within this widespread enzyme class.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 38","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202512449","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Organische Spinzustand-Photoschalter","authors":"Takuma Miyamura,&nbsp;Joël Schlecht,&nbsp;Prof. Dr. Oliver Dumele","doi":"10.1002/ange.202512691","DOIUrl":"https://doi.org/10.1002/ange.202512691","url":null,"abstract":"&lt;p&gt;Die präzise Kontrolle chemischer und physikalischer Eigenschaften molekularer Einheiten gehört zweifellos zu den ältesten Herausforderungen und Motivationen der Wissenschaft. Maßgeschneiderte Aktor–Antwort-Systeme können für unterschiedlichste Anforderungen entwickelt werden. Eine besonders interessante molekulare Eigenschaft ist der elektronische Spinzustand &lt;i&gt;S&lt;/i&gt;, der die Spin-Multiplizität 2&lt;i&gt;S&lt;/i&gt; + 1 eines Atoms, Moleküls oder Komplexes bestimmt.&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;1, 2&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; Die meisten organischen Moleküle und anorganischen Hauptgruppensysteme besitzen eine geschlossene Elektronenkonfiguration (&lt;i&gt;S&lt;/i&gt; = 0). Übergangsmetallkomplexe zeigen häufig unterschiedliche Spin-Multiplizitäten, wie sie sich aus der Ligandenfeldtheorie ergeben, mit niedrig- oder hochspinigen Konfigurationen abhängig von der Koordinationsumgebung.&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;3&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; Die reversible Änderung der Elektronenkonfiguration kann durch Spin-Crossover-Komplexe erreicht werden. Obwohl dieses Gebiet hochaktuell ist und viele Beiträge hervorgebracht hat, wurden Systeme mit metallbasiertem Spin bereits umfassend behandelt. &lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;4-10&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt;&lt;/p&gt;&lt;p&gt;Stabile und rein organische Moleküle befinden sich in der Regel in einer festgelegten geschlossenen Elektronenkonfiguration. π-Systeme mit offenem Schalencharakter wurden entwickelt, deren elektronische Struktur häufig durch die Prinzipien der Aromatizität bestimmt wird.&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;11-18&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; Eine Ausnahme von der allgemeinen Tendenz zu geschlossenen Schalen bei organischen Molekülen bilden nicht-Kekulé-Kohlenwasserstoffe, von denen einige unter Umgebungsbedingungen stabile offen-schale Diradikalstrukturen zeigen.&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;19-23&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; Darüber hinaus sind eine Reihe stabiler organischer Aminoxylradikale,&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;24-27&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; Triphenylmethylradikale,&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;28-30&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; allylischer Radikale&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;31-35&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; und anderer Strukturen mit dauerhaft offener Schale bekannt.&lt;sup&gt;[&lt;/sup&gt;&lt;span&gt;&lt;sup&gt;36-41&lt;/sup&gt;&lt;/span&gt;&lt;sup&gt;]&lt;/sup&gt; Die Änderung des Spinzustands organischer Systeme ist eine Herausforderung, insbesondere wenn sie reversibel durch einen äußeren Reiz ausgelöst werden soll (Abbildung 1). Die Vielseitigkeit eines vollständig organischen Designs ermöglicht es jedoch, gezielt Eigenschaften wie den Spin–Spin-Abstand und die spezifische Anpassung des Auslösers (z. B. der Wellenlänge) für den Spin-Schalter anzusprechen, wodurch leichte, ungiftige und flexiblere Materialien entstehen, die den Strukturraum metallhaltiger Systeme übertreffen.(Elektronische Zusatzinformation)&lt;/p&gt;&lt;p&gt;Beide Kategorien weisen herausragende Beispiele auf, deren molekulares Design und Schaltverhalten im Verlauf dieser Übersicht diskutiert werden.&lt;/p&gt;&lt;p&gt;Bis heute wurde eine Reihe von Methoden zur Charakterisierung und Ana","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 38","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202512691","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring the Oxygen Vacancy Distribution in Se-Doped RuOx to Enhance Its Stability in Acidic Water Electrolysis","authors":"Yongping Yang,&nbsp;Shulin Wang,&nbsp;Guikai Zhang,&nbsp;Xingyu Li,&nbsp;Qikai Wu,&nbsp;Hao Liu,&nbsp;Ziliang Deng,&nbsp;Xinyi Han,&nbsp;Prof. Shuailong Zhang,&nbsp;Wenbo Dong,&nbsp;Jiangnan Song,&nbsp;Prof. Yabin Chen,&nbsp;Prof. Xiao Gao,&nbsp;Prof. Yao Yang,&nbsp;Prof. Juncai Dong,&nbsp;Prof. Liang Cao,&nbsp;Prof. Zipeng Zhao","doi":"10.1002/ange.202512848","DOIUrl":"https://doi.org/10.1002/ange.202512848","url":null,"abstract":"<p>Developing durable ruthenium (Ru)-based catalysts for proton exchange membrane water electrolyzer (PEMWE) remains challenging due to irreversible Ru dissolution and lattice oxygen instability. Although elemental doping is a general method to improve stability, it inadvertently induces oxygen vacancies (V_Os), which are randomly distributed in the nanocatalyst. Notably, the impact of V_O distribution on the stability of Ru-based catalysts remains unresolved. Herein, we synthesized the Se-doped Ru oxide via annealing the mixture of ruthenium (III) chloride and selenium (Se) in the air (Ur-Se-RuO_x) with the presence of urea, showing the V_Os distributed away from Se dopants, which is significantly different from the Se-doped Ru oxide synthesized without urea (Se-RuO_x), showing V_Os distributed relatively close to the Se dopants. The Ur-Se-RuO_x demonstrates superior oxygen evolution reaction performance over Se-RuO_x. Particularly, Ur-Se-RuO_x delivers a low working voltage (1.62 V@1 A cm⁻²) and excellent durability (&gt;1000 h@200 mA cm⁻²) in PEMWE tests. Experimental and theoretical results reveal that V_Os engage in long-range cooperation with spatially decoupled Se dopants in Ur-Se-RuO_x, synergistically enhancing reaction kinetics via an intramolecular oxygen coupling mechanism, while inhibiting the lattice oxygen mechanism and suppressing Ru dissolution, which demonstrates a new strategy to break the activity–stability trade-off in promising Ru-based catalysts.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Light-Gated Amine Exchange in Diarylethene-Crosslinked Microgels","authors":"Kevin Broi,&nbsp;Frédéric Grabowski,&nbsp;Sarah Esser,&nbsp;Jannick Dörr,&nbsp;Prof.Dr. Andrij Pich,&nbsp;Prof. Stefan Hecht","doi":"10.1002/ange.202510141","DOIUrl":"10.1002/ange.202510141","url":null,"abstract":"<p>The functionalization of microgels with photoswitchable moieties enables the construction of multi-responsive systems, which are highly interesting for biological applications, for example, in drug delivery. Controlling the reversible uptake of functional molecules, however, remains a major challenge. To address this, we developed a novel aniline-type diarylethene (DAE) crosslinker and prepared a series of corresponding poly(<i>N</i>-vinylcaprolactam)-based microgels with varying degrees of DAE crosslinker. Upon UV light irradiation, the aniline (and thus enamine) motif of the DAE is converted to its imine form, thus allowing for reversible exchange with primary amines. Irradiating the DAE with blue light covalently locks the equilibrium and traps the amine in the microgels. The light-controlled covalent binding of fluorinated, hydrophobic, and hydrophilic amine derivatives was proven by dynamic light scattering and ¹⁹F NMR spectroscopy. Importantly, the impact of photoisomerization and amine binding on microgel properties was investigated and we were able to remotely control size as well as temperature and pH responsiveness by light. Overall, this study demonstrates optically gated uptake and release of functional amines in multi-responsive microgels and highlights their potential biological applications.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 39","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202510141","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129211","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polysulfamates as “Macroisosteres” of Polyurethanes with Improved Degradability","authors":"Srutashini Das,&nbsp;Dr. Katarzyna Doktor,&nbsp;Dr. Biswajit Saha,&nbsp;Dr. Felipe Cesar Sousa e Silva,&nbsp;Rachel M. Wynn,&nbsp;Prof. Dr. Quentin Michaudel","doi":"10.1002/ange.202510841","DOIUrl":"10.1002/ange.202510841","url":null,"abstract":"<p>Addressing the environmental persistence of plastics requires the development of next-generation polymers that combine high performance with enhanced degradability. Progress toward this grand challenge has been impeded, in part, by the absence of a general blueprint for the macromolecular design of such materials. Herein, we introduce a “macroisostere” design strategy, where the carbonyl group (–CO–) in polyurethanes (PUs) is replaced with a sulfonyl group (–SO₂–), resulting in a virtually unknown family of polymers called polysulfamates. This approach, inspired by the use of bioisosteres in drug discovery, aims to preserve key interchain interactions that contribute to thermomechanical performance while enhancing the hydrolytic lability of the polymer backbone. The optimization of a Sulfur(VI) Fluoride Exchange (SuFEx) polymerization allowed the synthesis of ten polysulfamates structurally analogous to common PUs. Comparative analysis of one PU and its polysulfamate analog showed that this isosteric substitution increases thermal stability, slightly lowers the glass transition temperature, and retains similar hardness and reduced Young's modulus. Notably, the S(VI)-based polysulfamate demonstrated significantly enhanced hydrolytic degradability. These results highlight the potential of the “macroisostere” approach as a generalizable strategy for designing high-performance, degradable alternatives to traditional plastics.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 39","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202510841","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorine···π Induced Alkyne Concentrating and Orderly Arranged Sulfonate-Adjusted Interfacial Water Structure Promote Alkene Electrosynthesis at Large Current Densities","authors":"Haotian Wang,&nbsp;Meng He,&nbsp;Dr. Rui Li,&nbsp;Yunjia Liu,&nbsp;Dr. Ying Gao,&nbsp;Prof. Bin Zhang,&nbsp;Prof. Cuibo Liu","doi":"10.1002/ange.202513463","DOIUrl":"https://doi.org/10.1002/ange.202513463","url":null,"abstract":"<p>Electrocatalytic semihydrogenation of alkynes to alkenes with water at nearly industrial current densities is highly important. However, a low interfacial alkyne–water ratio leads to severe hydrogen evolution, making it extremely challenging to obtain alkenes with a high Faradaic efficiency (FE). Here, a strategy involving fluorine···π interaction-induced alkyne concentration and orderly arranged sulfonate-repelled interfacial water-cation is developed over commercial Nafion-modified palladium nanotips, enabling electrolysis of 2-methyl-3-buten-2-ol (MBE) with up to 83% FE under −100 mA cm⁻². The fluorine···π effect concentrates the alkyne via its adsorption enhancement, promotes electron transfer, and lowers the activation energy, thus accelerating hydrogenation kinetics. Under the bias potential, the side chain of Nafion undergoing rearrangement from disordered to nearly ordered significantly decreases the interfacial free water coverage and activity, thereby reducing the amount of in situ-generated surface-active hydrogen, which contributes to suppressing hydrogen evolution and improving the FE. An 82% FE and 18.9 mmol h⁻¹ reaction rate of MBE is achieved in a 10 h continuous electrosynthesis at 1.25 A, demonstrating potential utility. Furthermore, the hydrogenation and deuteration of different alkynes with improved Faradaic efficiencies at −100 mA cm⁻² rationalize the design concept.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Corral[n]Bicarbazoles: Redox-Active Chiral Macrocycles for Air-Stable Radical Cations Formation and Guest Capture/Release","authors":"Ruiguo Wang,&nbsp;Dr. Han Han,&nbsp;Li-Bo Jing,&nbsp;Peng-Yao Shen,&nbsp;Xiao Xiao,&nbsp;Jia-Ying Deng,&nbsp;Qi Zhang,&nbsp;Haiting Di,&nbsp;Prof.Dr. Dong-Sheng Guo,&nbsp;Prof.Dr. Kang Cai","doi":"10.1002/ange.202511366","DOIUrl":"https://doi.org/10.1002/ange.202511366","url":null,"abstract":"<p>Macrocyclic compounds are pivotal in both supramolecular chemistry and materials science, as their preorganized cavities enable selective molecular recognition, while their cyclic frameworks facilitate electronic and spatial coupling of monomeric units to yield advanced optoelectronic and magnetic properties. However, macrocycles that combine exceptional host–guest recognition with these properties remain rare and challenging to design. Herein, we report the synthesis of three pairs of enantiopure, redox-active, conjugated macrocycles, termed corral[<i>n</i>]bicarbazole, employing axially chiral 4,4′-bicarbazole units. These macrocycles display strong blue emission (quantum yields up to 78% in THF) and pronounced circularly polarized luminescence (|<i>g</i>_lum| up to 10⁻³). Notably, controlled oxidation of corral[<i>n</i>]bicarbazoles generates their mono- and polyradical cations with exceptional air stability (half-lives up to five days) and intriguing magnetic properties. The electron-rich deep-cavity of corral[4]bicarbazole confers strong hosting ability (<i>K</i>_a = 10⁴–10⁵ M⁻¹) toward cationic guests, facilitating redox-responsive guest capture/release. By integrating a chiroptical, redox-active backbone with a switchable recognition cavity, corral[<i>n</i>]bicarbazoles offer a versatile platform for advancing interdisciplinary innovation, with potential applications in optoelectronics, spintronics, and smart supramolecular materials.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Asymmetric Catalytic 1,2-Azaarene Migration to α-Azaaryl-α-Hydroxy Esters Enabled by a Tailored Ligand","authors":"Xing-Zi Li,&nbsp;Yue-Hai Xu,&nbsp;Fang-Zhou Li,&nbsp;Yu-Ping He,&nbsp;Prof. Dr. Hua Wu","doi":"10.1002/ange.202511791","DOIUrl":"https://doi.org/10.1002/ange.202511791","url":null,"abstract":"<p>Despite their prevalence in bioactive molecules, the stereoselective construction of α-azaaryl-α-hydroxycarboxylates remains a formidable challenge. Notably, although the benzilic ester rearrangement (BER) is an efficient approach to α-hydroxycarboxylates, asymmetric catalytic BER remains poorly developed, largely due to poor stereorecognition of the vicinal diketone substituents by common chiral catalysts. In response to these issues, here we report a copper-catalyzed asymmetric BER of azaarene-derived 1,2-diketones with simple alcohols to give diverse α-azaaryl-α-hydroxy esters. It is proposed that the azaarene nitrogen and the adjacent carbonyl group chelate copper to form a five-membered metallacycle, initiating the subsequent stereoselective 1,2-nucleophilic addition step. Meanwhile, enantiocontrol over vicinal diketones was achieved by a tailored bisoxazoline (BOX) ligand with two rigid, long, and terminally bulky sidearms. This study overcomes the incompatibility between azaarenes and BOX ligands, and also unlocks asymmetric catalytic 1,2-azaarene migrations.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}