Pub Date : 2026-03-26DOI: 10.1016/j.chempr.2026.102993
Ofek Vardi, Nir Yuran, Ella Manuela Jakob, Gili Ben-Nissan, Shira Yochelis, Michal Sharon, Yossi Paltiel
Distinct isotopic fractionation in biomolecules, compared with atmospheric values, reflects their biosynthetic origin. Monitoring these fractionation changes offers a valuable approach for probing early metabolic networks. A key question in the study of life’s origins is the role of electronic spin and magnetic surfaces in symmetry breaking and the emergence of homochirality. Here, we used magnetic filters to show that the dynamical interaction with the magnetic surfaces changes the isotope fractions of 13C L-methionine compared with 12C L-methionine. Specifically, mass spectrometry analysis reveals that the isotopic fractionation of both natural and ¹³C-enriched L-methionine is influenced by electron spin-dependent interactions.
与大气值相比，生物分子中不同的同位素分馏反映了它们的生物合成来源。监测这些分馏变化为探测早期代谢网络提供了一种有价值的方法。研究生命起源的一个关键问题是电子自旋和磁性表面在对称破缺和同手性出现中的作用。在这里，我们使用磁性过滤器来证明与磁性表面的动态相互作用改变了13C l -蛋氨酸与12C l -蛋氨酸的同位素分数。具体来说，质谱分析表明，天然和¹³c富集的l -蛋氨酸的同位素分馏都受到电子自旋依赖相互作用的影响。
{"title":"Spin-dependent isotopic fractionation of L-methionine","authors":"Ofek Vardi, Nir Yuran, Ella Manuela Jakob, Gili Ben-Nissan, Shira Yochelis, Michal Sharon, Yossi Paltiel","doi":"10.1016/j.chempr.2026.102993","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102993","url":null,"abstract":"Distinct isotopic fractionation in biomolecules, compared with atmospheric values, reflects their biosynthetic origin. Monitoring these fractionation changes offers a valuable approach for probing early metabolic networks. A key question in the study of life’s origins is the role of electronic spin and magnetic surfaces in symmetry breaking and the emergence of homochirality. Here, we used magnetic filters to show that the dynamical interaction with the magnetic surfaces changes the isotope fractions of <sup>13</sup>C L-methionine compared with <sup>12</sup>C L-methionine. Specifically, mass spectrometry analysis reveals that the isotopic fractionation of both natural and ¹³C-enriched L-methionine is influenced by electron spin-dependent interactions.","PeriodicalId":268,"journal":{"name":"Chem","volume":"44 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-26DOI: 10.1016/j.chempr.2026.102989
Hongliang Ye, Andrew C.-H. Sue
Crystallization often limits the structural determination of flexible or scarce molecules. Reporting in the Journal of the American Chemical Society, Wang and co-workers demonstrate how a silver-based crystalline mate combined with in situ acetylation tagging converts stubborn molecules into co-crystallizable targets. Their method enables rapid NMR-tube crystallization and extends single-crystal X-ray diffraction to previously intractable compounds from minimal material.
{"title":"Coaxing stubborn molecules into crystals with a silver triangle","authors":"Hongliang Ye, Andrew C.-H. Sue","doi":"10.1016/j.chempr.2026.102989","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102989","url":null,"abstract":"Crystallization often limits the structural determination of flexible or scarce molecules. Reporting in the <em>Journal of the American Chemical Society</em>, Wang and co-workers demonstrate how a silver-based crystalline mate combined with <em>in situ</em> acetylation tagging converts stubborn molecules into co-crystallizable targets. Their method enables rapid NMR-tube crystallization and extends single-crystal X-ray diffraction to previously intractable compounds from minimal material.","PeriodicalId":268,"journal":{"name":"Chem","volume":"52 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-26DOI: 10.1016/j.chempr.2026.102992
Víctor Carratalá, Alechania Misturini, Moussa D. Faye Diouf, Rebecca Vismara, Alejandro Lamas, Mauro Gemmi, Natalia M. Padial, Carlos Martí-Gastaldo
Achieving chemical stability and conformational flexibility within adaptive porous materials built from peptide bonds and amino acid chemistry remains a significant challenge in framework design. Here, we introduce an alternative synthetic platform that employs bispyrazolate amino acid dipeptides, enabling the integration of short, conformationally flexible peptides into pyrazolate frameworks built from rigid rod-type [Zn(μ2-Pz)2] secondary building units. The nature of the amino acid side chain dictates both the dimensionality and the adaptive response of the resulting frameworks, allowing the controlled assembly of either three-dimensional (MUV-A) or layered two-dimensional (MUV-F and MUV-Y) architectures. Solvent-induced transformations reveal a continuum of dynamic responses, ranging from highly flexible reopening in MUV-A to solvent-selective switching in MUV-Y, governed by the interplay between backbone conformational freedom and host-guest interactions. This work establishes a general synthetic platform to program the dynamic behavior of chemically robust peptide-based frameworks, bridging reticular design with programmable adaptive porosity.
{"title":"Synthetic amino acids for programming adaptive response in pyrazolate peptide frameworks","authors":"Víctor Carratalá, Alechania Misturini, Moussa D. Faye Diouf, Rebecca Vismara, Alejandro Lamas, Mauro Gemmi, Natalia M. Padial, Carlos Martí-Gastaldo","doi":"10.1016/j.chempr.2026.102992","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102992","url":null,"abstract":"Achieving chemical stability and conformational flexibility within adaptive porous materials built from peptide bonds and amino acid chemistry remains a significant challenge in framework design. Here, we introduce an alternative synthetic platform that employs bispyrazolate amino acid dipeptides, enabling the integration of short, conformationally flexible peptides into pyrazolate frameworks built from rigid rod-type [Zn(<em>μ</em><sub><em>2</em></sub>-Pz)<sub>2</sub>] secondary building units. The nature of the amino acid side chain dictates both the dimensionality and the adaptive response of the resulting frameworks, allowing the controlled assembly of either three-dimensional (MUV-A) or layered two-dimensional (MUV-F and MUV-Y) architectures. Solvent-induced transformations reveal a continuum of dynamic responses, ranging from highly flexible reopening in MUV-A to solvent-selective switching in MUV-Y, governed by the interplay between backbone conformational freedom and host-guest interactions. This work establishes a general synthetic platform to program the dynamic behavior of chemically robust peptide-based frameworks, bridging reticular design with programmable adaptive porosity.","PeriodicalId":268,"journal":{"name":"Chem","volume":"6 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507694","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The strong growth in the consumption of natural gas is mainly due to its use as a fuel for energy and as a feedstock for industrial processes because it is a cleaner source than coal and oil. Because of this feature, there have been great efforts for the development of efficient technologies for methane conversion for a long time. The fundamental challenges for methane conversion are its stable molecular architecture—with the strongest known C–H bonds—and its lower activation energy than any molecular product of methane. Recently, zeolite-based catalysts with unique features of selective adsorption, precise assembly of active sites, and controllable composition have garnered considerable attention for methane conversions, such as methane dehydroaromatization (MDA), dry reforming of methane (DRM), partial oxidation of methane, complete oxidation of methane, and the selective catalytic reduction of NOx (CH4-SCR). This perspective briefly summarizes recent results from methane conversions, provides a couple examples of efficient methane conversion, and proposes the challenges and opportunities over zeolite-based catalysts, which should be helpful for the comprehensive utilization of methane and carbon neutrality in the future.
{"title":"Zeolite-based catalysts for methane conversion: Challenges and opportunities","authors":"Feng Li, Yuan Fang, Yaqi Lai, Liang Wang, Xiangju Meng, Feng-Shou Xiao","doi":"10.1016/j.chempr.2026.102986","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102986","url":null,"abstract":"The strong growth in the consumption of natural gas is mainly due to its use as a fuel for energy and as a feedstock for industrial processes because it is a cleaner source than coal and oil. Because of this feature, there have been great efforts for the development of efficient technologies for methane conversion for a long time. The fundamental challenges for methane conversion are its stable molecular architecture—with the strongest known C–H bonds—and its lower activation energy than any molecular product of methane. Recently, zeolite-based catalysts with unique features of selective adsorption, precise assembly of active sites, and controllable composition have garnered considerable attention for methane conversions, such as methane dehydroaromatization (MDA), dry reforming of methane (DRM), partial oxidation of methane, complete oxidation of methane, and the selective catalytic reduction of NO<sub><em>x</em></sub> (CH<sub>4</sub>-SCR). This perspective briefly summarizes recent results from methane conversions, provides a couple examples of efficient methane conversion, and proposes the challenges and opportunities over zeolite-based catalysts, which should be helpful for the comprehensive utilization of methane and carbon neutrality in the future.","PeriodicalId":268,"journal":{"name":"Chem","volume":"38 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-20DOI: 10.1016/j.chempr.2026.102959
Tobias Randt, Hendrik F.T. Klare, Martin Oestreich
Neutral main-group Lewis acids are established catalysts for a broad range of transformations in synthetic chemistry. Cationic versions thereof have become accessible with the advent of weakly coordinating anions (WCAs), also enabling the isolation of highly Lewis acidic intermediates. One such example is the family of tetravalent silicon cations often called silylium ions. Despite their stabilization by these counteranions or by an arene solvent, these fleeting intermediates are nevertheless characterized by an exceptionally high Lewis acidity. Their inherent halophilic nature equips them with the ability to activate even the most inert carbon–halogen bonds, thereby generating various reactive intermediates, such as carbenium ions and super Brønsted acidic Wheland complexes. In this perspective, our aim is to introduce the concept of The Cation Shuffle, where an interplay between silylium ions, carbenium ions, and Brønsted acidic arenium ions can be turned into meaningful chemical transformations. The underlying mechanisms of recently reported reactions will be discussed.
{"title":"The Cation Shuffle: Interplay of silylium, carbenium, and arenium ions in superelectrophile catalysis","authors":"Tobias Randt, Hendrik F.T. Klare, Martin Oestreich","doi":"10.1016/j.chempr.2026.102959","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102959","url":null,"abstract":"Neutral main-group Lewis acids are established catalysts for a broad range of transformations in synthetic chemistry. Cationic versions thereof have become accessible with the advent of weakly coordinating anions (WCAs), also enabling the isolation of highly Lewis acidic intermediates. One such example is the family of tetravalent silicon cations often called silylium ions. Despite their stabilization by these counteranions or by an arene solvent, these fleeting intermediates are nevertheless characterized by an exceptionally high Lewis acidity. Their inherent halophilic nature equips them with the ability to activate even the most inert carbon–halogen bonds, thereby generating various reactive intermediates, such as carbenium ions and super Brønsted acidic Wheland complexes. In this perspective, our aim is to introduce the concept of <em>The Cation Shuffle</em>, where an interplay between silylium ions, carbenium ions, and Brønsted acidic arenium ions can be turned into meaningful chemical transformations. The underlying mechanisms of recently reported reactions will be discussed.","PeriodicalId":268,"journal":{"name":"Chem","volume":"79 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-20DOI: 10.1016/j.chempr.2026.102957
Indrajit Paul, Attila Csomos, Krzysztof A. Konieczny, Roberto Chavez, Zoltán Mucsi, Levente Cseri, Balázs József Rózsa, Miguel A. Garcia-Garibay
We report here a Dewar-benzene-1,2-dicarboxylic-acid monoester with a 7-hydroxycoumarin (7H) fluorescent cage (DB-7HC) that leverages two-photon excitation (TPE) to trigger an adiabatic triplet-state reaction that initiates a quantum chain capable of releasing up to 400 molecules of 7HC per excitation event. The chemical enhancement afforded by a TPE microscope enables precise, chemically amplified uncaging, which together with sensitive fluorescence detection results in high three-dimensional (3D) spatial resolution. Using a femtosecond pulse laser operating in the 690- to 770-nm range, this system allows for deep bulk activation with minimal scattering, with 7HC acting as a TPE antenna and triplet sensitizer and, once released, as a fluorescent reporter for real-time imaging. The high quantum yield and solid-state reactivity of the Dewar-benzene-1,2-dicarboxylic-acid monoester motif make it a promising probe for 3D microfabrication, patterning, optogenetics, and targeted drug delivery, with a demonstrated 1- to 5-μm spatial resolution.
{"title":"Three-dimensional imaging via quantum chain amplification in a crystalline two-photon adiabatic photocage","authors":"Indrajit Paul, Attila Csomos, Krzysztof A. Konieczny, Roberto Chavez, Zoltán Mucsi, Levente Cseri, Balázs József Rózsa, Miguel A. Garcia-Garibay","doi":"10.1016/j.chempr.2026.102957","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102957","url":null,"abstract":"We report here a Dewar-benzene-1,2-dicarboxylic-acid monoester with a 7-hydroxycoumarin (7H) fluorescent cage (DB-7HC) that leverages two-photon excitation (TPE) to trigger an adiabatic triplet-state reaction that initiates a quantum chain capable of releasing up to 400 molecules of 7HC per excitation event. The chemical enhancement afforded by a TPE microscope enables precise, chemically amplified uncaging, which together with sensitive fluorescence detection results in high three-dimensional (3D) spatial resolution. Using a femtosecond pulse laser operating in the 690- to 770-nm range, this system allows for deep bulk activation with minimal scattering, with 7HC acting as a TPE antenna and triplet sensitizer and, once released, as a fluorescent reporter for real-time imaging. The high quantum yield and solid-state reactivity of the Dewar-benzene-1,2-dicarboxylic-acid monoester motif make it a promising probe for 3D microfabrication, patterning, optogenetics, and targeted drug delivery, with a demonstrated 1- to 5-μm spatial resolution.","PeriodicalId":268,"journal":{"name":"Chem","volume":"13 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The integrated electrochemical-microbial system (iEMS) is a promising strategy for converting CO2 into high-value bioproducts. However, the mismatch in the carbon species and flux between electrocatalysis and microbial metabolism hinders its overall efficiency. Herein, we develop a scalable Ag/Cu metal superlattice (MSL@Ag/Cu) electrocatalyst with a periodic electric-potential gradient, which enables the selective and stable production of microbe-biased ethanol substrate and maintains carbon flux for the iEMS. The directional Ag/Cu configuration causes a spatial confinement effect, which enriches and holds the key intermediates for sustainable C–C coupling. MSL@Ag/Cu achieves a high Faradaic efficiency of ethanol (>61.1%) and maintains this efficiency for over 220 h at 200 mA cm−2 in an industrial electrolyzer. This long-term ethanol yield (160 mmol L−1) with indispensable carbon flux of Saccharomyces cerevisiae enables the breakthrough conversion of CO2 to bioproducts. Techno-economic analysis indicates that the iEMS generates a profit of $15.5 million per year, which is 15-fold that of traditional electrocatalytic synthesis.
{"title":"Superlattice electrocatalysis matching microbial metabolism for sustainable CO2-to-bioproduct conversion","authors":"Miao Liu, Yanfeng Shi, Hao Shi, Peilin Huang, Lupeng Wang, Zhujun Fu, Tianming Wu, Yuanhong Xu","doi":"10.1016/j.chempr.2026.102955","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102955","url":null,"abstract":"The integrated electrochemical-microbial system (iEMS) is a promising strategy for converting CO<sub>2</sub> into high-value bioproducts. However, the mismatch in the carbon species and flux between electrocatalysis and microbial metabolism hinders its overall efficiency. Herein, we develop a scalable Ag/Cu metal superlattice (MSL@Ag/Cu) electrocatalyst with a periodic electric-potential gradient, which enables the selective and stable production of microbe-biased ethanol substrate and maintains carbon flux for the iEMS. The directional Ag/Cu configuration causes a spatial confinement effect, which enriches and holds the key intermediates for sustainable C–C coupling. MSL@Ag/Cu achieves a high Faradaic efficiency of ethanol (>61.1%) and maintains this efficiency for over 220 h at 200 mA cm<sup>−2</sup> in an industrial electrolyzer. This long-term ethanol yield (160 mmol L<sup>−1</sup>) with indispensable carbon flux of <em>Saccharomyces cerevisiae</em> enables the breakthrough conversion of CO<sub>2</sub> to bioproducts. Techno-economic analysis indicates that the iEMS generates a profit of $15.5 million per year, which is 15-fold that of traditional electrocatalytic synthesis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"33 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-18DOI: 10.1016/j.chempr.2026.102954
Ya Gao, Pablo Ballester, Gantulga Norjmaa, Fahmi Himo, Julius Rebek, Yang Yu
Molecular assembly involves limiting the translational freedom of the participating compounds, but rotations and internal motions persist. This perspective describes the motions involved in cavitand complexes. In the literature, solution NMR studies have been used to reveal the spinning, tumbling, and rolling of rigid guests and the scrolling, folding, and coiling of flexible guests. An underappreciated yet widespread feature of cavitand complexation involves the reciprocal motions of the hosts. These dynamics allow moving partners to achieve configurations that are unlikely to occur with either component alone. Computational methods have likewise been applied to shed light on the dynamics of host-guest complexes.The fluid nature of these complexes is not captured by the lock-and-key or induced-fit model or by the preorganization formalism of supramolecular chemistry. Instead, we propose that the complexation behavior resembles a dance of host and guest. This dynamic fit navigates a shallow energy landscape, where weak intermolecular forces sustain low-barrier, coupled motions essential to the complex.
{"title":"Supradynamics: Motion in cavitand complexes","authors":"Ya Gao, Pablo Ballester, Gantulga Norjmaa, Fahmi Himo, Julius Rebek, Yang Yu","doi":"10.1016/j.chempr.2026.102954","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102954","url":null,"abstract":"Molecular assembly involves limiting the translational freedom of the participating compounds, but rotations and internal motions persist. This perspective describes the motions involved in cavitand complexes. In the literature, solution NMR studies have been used to reveal the spinning, tumbling, and rolling of rigid guests and the scrolling, folding, and coiling of flexible guests. An underappreciated yet widespread feature of cavitand complexation involves the reciprocal motions of the hosts. These dynamics allow moving partners to achieve configurations that are unlikely to occur with either component alone. Computational methods have likewise been applied to shed light on the dynamics of host-guest complexes.The fluid nature of these complexes is not captured by the lock-and-key or induced-fit model or by the preorganization formalism of supramolecular chemistry. Instead, we propose that the complexation behavior resembles a dance of host and guest. This dynamic fit navigates a shallow energy landscape, where weak intermolecular forces sustain low-barrier, coupled motions essential to the complex.","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1016/j.chempr.2026.102961
Longhuan Xie, Peijie Luo, Tao Lu, Weipeng Zheng, Yinyan Su, Jianbo Wang, Xiaotian Qi, Yan Xu
Boryl groups are central to modern synthetic chemistry, in particular because of their facile installation from various functional groups (FGs) and versatile transformations into diverse chemical bonds. Although the introduction and interconversion of boryl groups are well established, the direct repositioning of an existing boryl group along a carbon backbone—without any other pre-installed FGs—remains underexplored. Herein, we disclose a direct 1,2-boryl translocation reaction with common C(sp3)–H bonds in alkyl boronic esters. Driven by the synergy between hydrogen atom abstraction (HAA) and donation (HAD) catalysis, this reaction features reversible radical generation at multiple C–H sites yet ensures selective transformation via the kinetically favored 1,2-radical boryl migration. No directing groups (DGs) or stoichiometric reagents are needed, and the mechanism is supported by both experimental and computational evidence. By integrating on-demand boryl repositioning with boryl’s established synthetic versatility, this method further offers strategic opportunities for planning streamlined syntheses.
{"title":"1,2-Boryl/hydrogen transposition via reversible C–H sampling","authors":"Longhuan Xie, Peijie Luo, Tao Lu, Weipeng Zheng, Yinyan Su, Jianbo Wang, Xiaotian Qi, Yan Xu","doi":"10.1016/j.chempr.2026.102961","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102961","url":null,"abstract":"Boryl groups are central to modern synthetic chemistry, in particular because of their facile installation from various functional groups (FGs) and versatile transformations into diverse chemical bonds. Although the introduction and interconversion of boryl groups are well established, the direct repositioning of an existing boryl group along a carbon backbone—without any other pre-installed FGs—remains underexplored. Herein, we disclose a direct 1,2-boryl translocation reaction with common C(<em>sp</em><sup>3</sup>)–H bonds in alkyl boronic esters. Driven by the synergy between hydrogen atom abstraction (HAA) and donation (HAD) catalysis, this reaction features reversible radical generation at multiple C–H sites yet ensures selective transformation via the kinetically favored 1,2-radical boryl migration. No directing groups (DGs) or stoichiometric reagents are needed, and the mechanism is supported by both experimental and computational evidence. By integrating on-demand boryl repositioning with boryl’s established synthetic versatility, this method further offers strategic opportunities for planning streamlined syntheses.","PeriodicalId":268,"journal":{"name":"Chem","volume":"27 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1016/j.chempr.2026.102949
Hao Deng, Marco Bengsch, Christophe Farès, Zihang Qiu, Mir Henglin, Constanze N. Neumann
Solid-state nuclear magnetic resonance (NMR) spectroscopy can capture the chemical inequivalence of differently shaped metal-organic framework (MOF) pores. We show that the chemical shifts of reporting substituents that extend a defined distance into a MOF pore reflect the pore shape. Comparison of porous coordination network (PCN)-222, PCN-224, and PCN-223 demonstrates that the same linker and node provide three distinct chemical environments in the three different types of pores present in the MOFs. The chemical inequivalence of differently positioned substituents ensures that NMR spectroscopy can reveal into which pore post-synthetically added ligands are facing, without a need for single crystals, and even if only 10% of nodes are functionalized. The operational facility with which location-resolved information can be obtained permits NMR to shed light on the thermodynamics and kinetics of mixed-linker MOF growth, the presence of defects, and the dynamic behavior of added ligands.
{"title":"Solid-state NMR provides location-specific information on the chemical environment inside MOF pores","authors":"Hao Deng, Marco Bengsch, Christophe Farès, Zihang Qiu, Mir Henglin, Constanze N. Neumann","doi":"10.1016/j.chempr.2026.102949","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102949","url":null,"abstract":"Solid-state nuclear magnetic resonance (NMR) spectroscopy can capture the chemical inequivalence of differently shaped metal-organic framework (MOF) pores. We show that the chemical shifts of reporting substituents that extend a defined distance into a MOF pore reflect the pore shape. Comparison of porous coordination network (PCN)-222, PCN-224, and PCN-223 demonstrates that the same linker and node provide three distinct chemical environments in the three different types of pores present in the MOFs. The chemical inequivalence of differently positioned substituents ensures that NMR spectroscopy can reveal into which pore post-synthetically added ligands are facing, without a need for single crystals, and even if only 10% of nodes are functionalized. The operational facility with which location-resolved information can be obtained permits NMR to shed light on the thermodynamics and kinetics of mixed-linker MOF growth, the presence of defects, and the dynamic behavior of added ligands.","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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