Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102643
Jun-Jie Wang , Xing-Yuan Zhang , Jing-Yao Bai , Qian-Yi Liu , Jun Wen , Rong Zhu
Here, we report a dynamic mechanophore system enabled by Cu-catalyzed ring-opening condensation polymerization of propargyl cyclic carbonates, featuring a diyne backbone with mechanosensitive propargylic/benzyl C(sp3)-C(sp3) linkages and simultaneously unmasked hydroxy side chains. The weak C–C linkages generate stabilized mechanoradicals under stress, which recombine at ambient temperature. Meanwhile, the hydroxy side groups facilitate the seamless incorporation of macromolecular cross-linkers in polyurethane (PU) networks, yielding elastomers with enhanced tensile strength, toughness, and self-healing efficiency. Molecular weight-dependent mechanosensitivity suggests potential topological effects. This work provides an approach to high-performance dynamic networks with a sensitive mechanochemical response.
{"title":"Dynamic mechanoresponsive polymers enabled by ring-opening polymerization of cyclic propargyl carbonates","authors":"Jun-Jie Wang , Xing-Yuan Zhang , Jing-Yao Bai , Qian-Yi Liu , Jun Wen , Rong Zhu","doi":"10.1016/j.chempr.2025.102643","DOIUrl":"10.1016/j.chempr.2025.102643","url":null,"abstract":"<div><div>Here, we report a dynamic mechanophore system enabled by Cu-catalyzed ring-opening condensation polymerization of propargyl cyclic carbonates, featuring a diyne backbone with mechanosensitive propargylic/benzyl C(sp<sup>3</sup>)-C(sp<sup>3</sup>) linkages and simultaneously unmasked hydroxy side chains. The weak C–C linkages generate stabilized mechanoradicals under stress, which recombine at ambient temperature. Meanwhile, the hydroxy side groups facilitate the seamless incorporation of macromolecular cross-linkers in polyurethane (PU) networks, yielding elastomers with enhanced tensile strength, toughness, and self-healing efficiency. Molecular weight-dependent mechanosensitivity suggests potential topological effects. This work provides an approach to high-performance dynamic networks with a sensitive mechanochemical response.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102643"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516287","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102646
Jian-Xin Wang , Issatay Nadinov , Simil Thomas , Osama Shekhah , Xin Zhu , Tengyue He , Tengjiao He , Xiting Yuan , Shumei Wang , Hao Jiang , Osman M. Bakr , Husam N. Alshareef , Mohamed Eddaoudi , Omar F. Mohammed
In this study, we incorporate a small organic linker endowed with room-temperature phosphorescence properties into the metal-organic framework (MOF). The strong coordination and optimal proximity between the organic linker and heavy metal centers, along with the unique spatial arrangement of the linker, substantially enhance the efficiency of intersystem crossing and phosphorescence while suppressing the strong intermolecular π-π stacking typically observed in organic materials, thereby mitigating aggregation-caused quenching. This synergistic effect enables the efficient harvesting of triplet excitons and increases their radiative release by 50-fold. As a result, the MOF achieves more than a 50-fold enhancement in radioluminescence efficiency compared with the organic linker alone, along with a high X-ray imaging resolution of 20 lp/mm, surpassing most reported X-ray energy converters. These findings offer innovative design strategies for developing efficient MOF-based X-ray energy converters.
{"title":"An efficient metal-organic framework X-ray energy converter","authors":"Jian-Xin Wang , Issatay Nadinov , Simil Thomas , Osama Shekhah , Xin Zhu , Tengyue He , Tengjiao He , Xiting Yuan , Shumei Wang , Hao Jiang , Osman M. Bakr , Husam N. Alshareef , Mohamed Eddaoudi , Omar F. Mohammed","doi":"10.1016/j.chempr.2025.102646","DOIUrl":"10.1016/j.chempr.2025.102646","url":null,"abstract":"<div><div>In this study, we incorporate a small organic linker endowed with room-temperature phosphorescence properties into the metal-organic framework (MOF). The strong coordination and optimal proximity between the organic linker and heavy metal centers, along with the unique spatial arrangement of the linker, substantially enhance the efficiency of intersystem crossing and phosphorescence while suppressing the strong intermolecular π-π stacking typically observed in organic materials, thereby mitigating aggregation-caused quenching. This synergistic effect enables the efficient harvesting of triplet excitons and increases their radiative release by 50-fold. As a result, the MOF achieves more than a 50-fold enhancement in radioluminescence efficiency compared with the organic linker alone, along with a high X-ray imaging resolution of 20 lp/mm, surpassing most reported X-ray energy converters. These findings offer innovative design strategies for developing efficient MOF-based X-ray energy converters.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102646"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516259","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}
Enantioselective enzymes feature structured catalytic sites positioned within binding pockets. In contrast, widely occurring flat protein surfaces, which have been suggested to have emerged early in ancestral protein evolution as solvent-exposed β sheets, appear unlikely to catalyze asymmetric reactions because they lack the necessary scaffold for interacting with substrates in three dimensions. At the near-flat, water-accessible surface within the α-hemolysin transmembrane pore, we now demonstrate remarkable diastereoselectivity in hemithioacetal formation between a cysteine side chain and a series of aldehyde substrates. After protein surface remodeling by mutagenesis, diastereomeric ratios of up to 95:5 (kinetic control) and 98:2 (thermodynamic control) were achieved with a range of aromatic aldehydes. Molecular dynamics simulations confirmed asymmetric interactions between adducts and nearby side chains in a two-dimensional plane. Our findings indicate that flat protein surfaces can scaffold stereoselective chemistry, thereby expanding the designable protein space for catalyst engineering and providing insight into the origin of selective enzymes.
{"title":"Unexpected diastereoselective chemistry on a 2D protein surface","authors":"Zhong Hui Lim , Zonghua Bo , Emily Armstrong , Hagan Bayley , Yujia Qing","doi":"10.1016/j.chempr.2025.102717","DOIUrl":"10.1016/j.chempr.2025.102717","url":null,"abstract":"<div><div>Enantioselective enzymes feature structured catalytic sites positioned within binding pockets. In contrast, widely occurring flat protein surfaces, which have been suggested to have emerged early in ancestral protein evolution as solvent-exposed β sheets, appear unlikely to catalyze asymmetric reactions because they lack the necessary scaffold for interacting with substrates in three dimensions. At the near-flat, water-accessible surface within the α-hemolysin transmembrane pore, we now demonstrate remarkable diastereoselectivity in hemithioacetal formation between a cysteine side chain and a series of aldehyde substrates. After protein surface remodeling by mutagenesis, diastereomeric ratios of up to 95:5 (kinetic control) and 98:2 (thermodynamic control) were achieved with a range of aromatic aldehydes. Molecular dynamics simulations confirmed asymmetric interactions between adducts and nearby side chains in a two-dimensional plane. Our findings indicate that flat protein surfaces can scaffold stereoselective chemistry, thereby expanding the designable protein space for catalyst engineering and providing insight into the origin of selective enzymes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102717"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928638","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102630
Sangam Jha , Soumili Roy , Antara Reja , Ajeet Kumar Singh , Lisa Roy , Dibyendu Das
Early compartmentalized systems built from simple building blocks had to develop complex functions to self-sustain in a fluctuating environment under non-equilibrium conditions. Herein, we report the generation of membrane-bound confinements from the self-assembly of bolaamphiphile building blocks accessed via the spontaneous imine bond formation between two simple molecules: a dipeptide and a thermodynamically activated ester. The self-assembled vesicular structures demonstrated a native hydrolase-like activity, leading to the degradation of the ester bond of the building block (negative feedback) and subsequently to an autonomous disassembly. The dynamic vesicles could further demonstrate autopoietic behavior as they could promote the regeneration of its own building block from suitable precursors (positive feedback) by exploiting its native hydrolytic ability realized through a chemical reaction network.
{"title":"Non-equilibrium autopoietic vesicles driven by intrinsic catalysis","authors":"Sangam Jha , Soumili Roy , Antara Reja , Ajeet Kumar Singh , Lisa Roy , Dibyendu Das","doi":"10.1016/j.chempr.2025.102630","DOIUrl":"10.1016/j.chempr.2025.102630","url":null,"abstract":"<div><div><span>Early compartmentalized systems built from simple building blocks had to develop complex functions to self-sustain in a fluctuating environment under non-equilibrium conditions. Herein, we report the generation of membrane-bound confinements from the self-assembly of bolaamphiphile building blocks accessed via the spontaneous </span>imine<span> bond formation between two simple molecules: a dipeptide and a thermodynamically activated ester. The self-assembled vesicular structures demonstrated a native hydrolase-like activity, leading to the degradation of the ester bond of the building block (negative feedback) and subsequently to an autonomous disassembly. The dynamic vesicles could further demonstrate autopoietic behavior as they could promote the regeneration of its own building block from suitable precursors (positive feedback) by exploiting its native hydrolytic ability realized through a chemical reaction network.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102630"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341352","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102663
Jinqi Li , Huajie Zhu , Hanxiao Wang , Chenyang Zhao , Guanghui Ouyang , Minghua Liu
Although chiral nanostructures have been extensively studied, the fabrication of topological entities such as toroidal assemblies and their higher-order fused or catenated structures remains a formidable challenge. Here, we demonstrate a hierarchical assembly paradigm using a C3-symmetric benzene-1,3,5-tricarboxamide that enables the topological evolution of varied nanoarchitectures, such as discrete nanotoroids, fused super-nanotoroids containing up to 21 toroidal units, and nano-[2]catenanes. Our experimental and calculation results demonstrated that C3 molecules tended to form helical nanofibers with unexpected curvature due to both molecular chirality and bulky side chains. Further longitudinal extension and lateral lamellar packing of primary one-dimensional stacks led to the formation of dominant nanotoroids and stochastic nano-[2]catenanes with chiroptical signals and circularly polarized luminescence through an adaptive templating method. This work presents a cyclization-driven precise assembly of topologically discrete, fused, and catenated nanotoroids, unveiling the synergistic merging of chiral hierarchy and topological architectures in supramolecular self-assembly systems.
{"title":"Chiral C3-symmetric molecule assembly enabling topological nanotoroid, fused nanotoroid, and nanocatenane","authors":"Jinqi Li , Huajie Zhu , Hanxiao Wang , Chenyang Zhao , Guanghui Ouyang , Minghua Liu","doi":"10.1016/j.chempr.2025.102663","DOIUrl":"10.1016/j.chempr.2025.102663","url":null,"abstract":"<div><div>Although chiral nanostructures have been extensively studied, the fabrication of topological entities such as toroidal assemblies and their higher-order fused or catenated structures remains a formidable challenge. Here, we demonstrate a hierarchical assembly paradigm using a C3-symmetric benzene-1,3,5-tricarboxamide that enables the topological evolution of varied nanoarchitectures, such as discrete nanotoroids, fused super-nanotoroids containing up to 21 toroidal units, and nano-[2]catenanes. Our experimental and calculation results demonstrated that C3 molecules tended to form helical nanofibers with unexpected curvature due to both molecular chirality and bulky side chains. Further longitudinal extension and lateral lamellar packing of primary one-dimensional stacks led to the formation of dominant nanotoroids and stochastic nano-[2]catenanes with chiroptical signals and circularly polarized luminescence through an adaptive templating method. This work presents a cyclization-driven precise assembly of topologically discrete, fused, and catenated nanotoroids, unveiling the synergistic merging of chiral hierarchy and topological architectures in supramolecular self-assembly systems.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102663"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630084","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102714
Solhye Choe , Chaerin Lim , Sunghoon Kang , Eunsung Lee
The stabilization of organic radicals has long been a challenge due to their intrinsic reactivity. N-Heterocyclic carbenes (NHCs), with their unique electronic and steric properties, have emerged as powerful tools for stabilizing persistent radicals. This review highlights the latest advancements in carbene-supported organic radicals, covering key structural motifs, electronic properties, and implications for chemical reactivity. We discuss recent breakthroughs in the design of radical species derived from NHCs, cyclic (alkyl)(amino)carbenes (CAACs), and diamidocarbenes (DACs). The relationships among radical stability, spin delocalization, and functional applications are systematically discussed, particularly in the context of redox-active materials, photocatalysis, and electronic devices. This work underscores the broader significance of NHC-stabilized radicals in fundamental chemistry and applied sciences, offering insights into future directions for the field.
{"title":"N-Heterocyclic carbene-derived second-period main-group radicals: Synthesis, fundamentals, and applications","authors":"Solhye Choe , Chaerin Lim , Sunghoon Kang , Eunsung Lee","doi":"10.1016/j.chempr.2025.102714","DOIUrl":"10.1016/j.chempr.2025.102714","url":null,"abstract":"<div><div>The stabilization of organic radicals has long been a challenge due to their intrinsic reactivity. N-Heterocyclic carbenes (NHCs), with their unique electronic and steric properties, have emerged as powerful tools for stabilizing persistent radicals. This review highlights the latest advancements in carbene-supported organic radicals, covering key structural motifs, electronic properties, and implications for chemical reactivity. We discuss recent breakthroughs in the design of radical species derived from NHCs, cyclic (alkyl)(amino)carbenes (CAACs), and diamidocarbenes (DACs). The relationships among radical stability, spin delocalization, and functional applications are systematically discussed, particularly in the context of redox-active materials, photocatalysis, and electronic devices. This work underscores the broader significance of NHC-stabilized radicals in fundamental chemistry and applied sciences, offering insights into future directions for the field.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102714"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144987614","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102869
Xiang Li , Xiao Shen
Four-membered rings are valuable in drug discovery, but their functionalization is challenging. In a recent issue of Nature, Koh and co-workers report a photocatalytic method for the single-atom replacement of oxygen in oxetanes. This “ring-opening-closing” relay directly yields diverse azetidines, thietanes, and cyclobutanes, enabling late-stage skeletal editing of complex molecules and streamlined synthesis of drug intermediates.
{"title":"Photocatalytic single-atom replacement enables diversification of oxetanes to azetidines, thietanes, and cyclobutanes","authors":"Xiang Li , Xiao Shen","doi":"10.1016/j.chempr.2025.102869","DOIUrl":"10.1016/j.chempr.2025.102869","url":null,"abstract":"<div><div>Four-membered rings are valuable in drug discovery, but their functionalization is challenging. In a recent issue of <em>Nature</em>, Koh and co-workers report a photocatalytic method for the single-atom replacement of oxygen in oxetanes. This “ring-opening-closing” relay directly yields diverse azetidines, thietanes, and cyclobutanes, enabling late-stage skeletal editing of complex molecules and streamlined synthesis of drug intermediates.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102869"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718946","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}
We report the design of curved anthracene systems that undergo efficient Dewar isomerization upon visible-light absorption and release heat through thermally triggered reverse isomerization, with high cyclability. These systems achieve remarkably high-energy storage capacities—up to 170 kJ/mol and 0.65 MJ/kg—comparable to the best reported molecular solar thermal (MOST) materials, while offering the added capability of harnessing the standard solar spectrum and presenting chemical robustness. Notably, these curved anthracenes can be fine-tuned to store energy in a neat liquid state, presenting a promising route toward solvent-free solar thermal energy storage devices. This report highlights the potential of fully carbon-based aromatic systems to store a large quantity of solar energy via photo-induced valence isomerization and dearomatization.
{"title":"Curved anthracenes for visible-light photon energy storage via Dewar isomerization","authors":"Subhayan Chakraborty , Writam S.R. Choudhuri , Junichi Usuba , Qianfeng Qiu , Cijil Raju , Grace G.D. Han","doi":"10.1016/j.chempr.2025.102660","DOIUrl":"10.1016/j.chempr.2025.102660","url":null,"abstract":"<div><div>We report the design of curved anthracene systems that undergo efficient Dewar isomerization upon visible-light absorption and release heat through thermally triggered reverse isomerization, with high cyclability. These systems achieve remarkably high-energy storage capacities—up to 170 kJ/mol and 0.65 MJ/kg—comparable to the best reported molecular solar thermal (MOST) materials, while offering the added capability of harnessing the standard solar spectrum and presenting chemical robustness. Notably, these curved anthracenes can be fine-tuned to store energy in a neat liquid state, presenting a promising route toward solvent-free solar thermal energy storage devices. This report highlights the potential of fully carbon-based aromatic systems to store a large quantity of solar energy via photo-induced valence isomerization and dearomatization.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102660"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630248","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102825
Morgan Cordell , Andrei K. Yudin
In this perspective, we introduce the concept of isoreactivity—a framework for identifying structural modules that sustain a forward reaction path. By emphasizing functional roles within mechanisms, rather than electron count or frontier orbital similarity, isoreactivity captures parallels that elude existing classifications. We illustrate how this approach describes established trends in reactivity and points toward novel transformations. We hope that codifying isoreactivity will open new avenues for discovery, offering chemists an intuitive and pedagogically clear principle for guiding reaction design.
{"title":"Isoreactivity in chemistry","authors":"Morgan Cordell , Andrei K. Yudin","doi":"10.1016/j.chempr.2025.102825","DOIUrl":"10.1016/j.chempr.2025.102825","url":null,"abstract":"<div><div>In this perspective, we introduce the concept of isoreactivity—a framework for identifying structural modules that sustain a forward reaction path. By emphasizing functional roles within mechanisms, rather than electron count or frontier orbital similarity, isoreactivity captures parallels that elude existing classifications. We illustrate how this approach describes established trends in reactivity and points toward novel transformations. We hope that codifying isoreactivity will open new avenues for discovery, offering chemists an intuitive and pedagogically clear principle for guiding reaction design.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102825"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600131","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102665
Justin O.P. Waters , Elnaz Jamalzade , Hussein T. Abdulrazzaq , Nathaniel Kuch , Sampath R. Gunukula , James A. Dumesic , Philip J. Kersten , Thomas J. Schwartz
Many pharmaceuticals include chiral centers, which are introduced using high-cost building blocks such as (S)-3-hydroxy-γ-butyrolactone, (S)-HBL. This species is used in the synthesis of many important drugs, including statins, antibiotics, and HIV inhibitors, and it is currently produced from fossil resources via a high-cost, high-emission process. Here, we show that a nearly quantitative yield of enantiopure (S)-HBL can be obtained from glucose at ambient temperature, using a combination of biological and chemical catalysis. Whole-cell enzyme catalysis converts glucose to a labile intermediate (denoted as trione) that is subsequently reacted to (S)-HBL by metal-free homogeneous acid/base catalysis. These reactions do not involve the C5 of glucose, leading to enantiopure (S)-HBL, produced at less than half the present cost. This approach can also be used to produce other commercially important building blocks from sustainable feedstocks: the enzymes used for trione production are active in converting xylose, leading to the acrylate co-monomer 3-hydroxypropionic acid.
{"title":"Production of biorenewable, enantiopure (S)-3-hydroxy-γ-butyrolactone for pharmaceutical applications","authors":"Justin O.P. Waters , Elnaz Jamalzade , Hussein T. Abdulrazzaq , Nathaniel Kuch , Sampath R. Gunukula , James A. Dumesic , Philip J. Kersten , Thomas J. Schwartz","doi":"10.1016/j.chempr.2025.102665","DOIUrl":"10.1016/j.chempr.2025.102665","url":null,"abstract":"<div><div>Many pharmaceuticals include chiral centers, which are introduced using high-cost building blocks such as (S)-3-hydroxy-γ-butyrolactone, (S)-HBL. This species is used in the synthesis of many important drugs, including statins, antibiotics, and HIV inhibitors, and it is currently produced from fossil resources via a high-cost, high-emission process. Here, we show that a nearly quantitative yield of enantiopure (S)-HBL can be obtained from glucose at ambient temperature, using a combination of biological and chemical catalysis. Whole-cell enzyme catalysis converts glucose to a labile intermediate (denoted as trione) that is subsequently reacted to (S)-HBL by metal-free homogeneous acid/base catalysis. These reactions do not involve the C5 of glucose, leading to enantiopure (S)-HBL, produced at less than half the present cost. This approach can also be used to produce other commercially important building blocks from sustainable feedstocks: the enzymes used for trione production are active in converting xylose, leading to the acrylate co-monomer 3-hydroxypropionic acid.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102665"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652643","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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