Hydrogen bonds profoundly influence the fundamental chemical, physical and biological properties of molecules and materials. Owing to their relatively weaker interactions compared to other chemical bonds, hydrogen bonds alone are generally insufficient to induce substantial changes in electrical properties, thus imposing severe constraints on their applications in related devices. Here we report a metal–insulator transition controlled by hydrogen bonds for an organic–inorganic (1,3-diaminopropane)0.5SnSe2 superlattice that exhibits a colossal on–off ratio of 107 in electrical resistivity. The key to inducing the transition is a change in the amino group’s hydrogen-bonding structure from dynamic to static. In the dynamic state, thermally activated free rotation continuously breaks and forms transient hydrogen bonds with adjacent Se anions. In the static state, the amino group forms three fixed-angle positions, each separated by 120°. Our findings contribute to the understanding of electrical phenomena in organic–inorganic hybrid materials and may be used for the design of future molecule-based electronic materials.
{"title":"Dynamic-to-static switch of hydrogen bonds induces a metal–insulator transition in an organic–inorganic superlattice","authors":"Zhenkai Xie, Rui Luo, Tianping Ying, Yurui Gao, Boqin Song, Tongxu Yu, Xu Chen, Munan Hao, Congcong Chai, Jiashu Yan, Zhiheng Huang, Zhiguo Chen, Luojun Du, Chongqin Zhu, Jiangang Guo, Xiaolong Chen","doi":"10.1038/s41557-024-01566-1","DOIUrl":"https://doi.org/10.1038/s41557-024-01566-1","url":null,"abstract":"<p>Hydrogen bonds profoundly influence the fundamental chemical, physical and biological properties of molecules and materials. Owing to their relatively weaker interactions compared to other chemical bonds, hydrogen bonds alone are generally insufficient to induce substantial changes in electrical properties, thus imposing severe constraints on their applications in related devices. Here we report a metal–insulator transition controlled by hydrogen bonds for an organic–inorganic (1,3-diaminopropane)<sub>0.5</sub>SnSe<sub>2</sub> superlattice that exhibits a colossal on–off ratio of 10<sup>7</sup> in electrical resistivity. The key to inducing the transition is a change in the amino group’s hydrogen-bonding structure from dynamic to static. In the dynamic state, thermally activated free rotation continuously breaks and forms transient hydrogen bonds with adjacent Se anions. In the static state, the amino group forms three fixed-angle positions, each separated by 120°. Our findings contribute to the understanding of electrical phenomena in organic–inorganic hybrid materials and may be used for the design of future molecule-based electronic materials.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":21.8,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980822","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 : 2024-08-13DOI: 10.1038/s41557-024-01625-7
Fabian B. H. Rehm, Tristan J. Tyler, Yan Zhou, Yen-Hua Huang, Conan K. Wang, Nicole Lawrence, David J. Craik, Thomas Durek
{"title":"Author Correction: Repurposing a plant peptide cyclase for targeted lysine acylation","authors":"Fabian B. H. Rehm, Tristan J. Tyler, Yan Zhou, Yen-Hua Huang, Conan K. Wang, Nicole Lawrence, David J. Craik, Thomas Durek","doi":"10.1038/s41557-024-01625-7","DOIUrl":"10.1038/s41557-024-01625-7","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-024-01625-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141976180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-13DOI: 10.1038/s41557-024-01615-9
Atanu Ghosh, Jonathan T Yarranton, James K McCusker
{"title":"Publisher Correction: Establishing the origin of Marcus-inverted-region behaviour in the excited-state dynamics of cobalt(III) polypyridyl complexes.","authors":"Atanu Ghosh, Jonathan T Yarranton, James K McCusker","doi":"10.1038/s41557-024-01615-9","DOIUrl":"10.1038/s41557-024-01615-9","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141976181","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 : 2024-08-13DOI: 10.1038/s41557-024-01601-1
Evert Njomen, Rachel E. Hayward, Kristen E. DeMeester, Daisuke Ogasawara, Melissa M. Dix, Tracey Nguyen, Paige Ashby, Gabriel M. Simon, Stuart L. Schreiber, Bruno Melillo, Benjamin F. Cravatt
Covalent chemistry is a versatile approach for expanding the ligandability of the human proteome. Activity-based protein profiling (ABPP) can infer the specific residues modified by electrophilic compounds through competition with broadly reactive probes. However, the extent to which such residue-directed platforms fully assess the protein targets of electrophilic compounds in cells remains unclear. Here we evaluate a complementary protein-directed ABPP method that identifies proteins showing stereoselective reactivity with alkynylated, chiral electrophilic compounds—termed stereoprobes. Integration of protein- and cysteine-directed data from cancer cells treated with tryptoline acrylamide stereoprobes revealed generally well-correlated ligandability maps and highlighted features, such as protein size and the proteotypicity of cysteine-containing peptides, that explain gaps in each ABPP platform. In total, we identified stereoprobe binding events for >300 structurally and functionally diverse proteins, including compounds that stereoselectively and site-specifically disrupt MAD2L1BP interactions with the spindle assembly checkpoint complex leading to delayed mitotic exit in cancer cells.
{"title":"Multi-tiered chemical proteomic maps of tryptoline acrylamide–protein interactions in cancer cells","authors":"Evert Njomen, Rachel E. Hayward, Kristen E. DeMeester, Daisuke Ogasawara, Melissa M. Dix, Tracey Nguyen, Paige Ashby, Gabriel M. Simon, Stuart L. Schreiber, Bruno Melillo, Benjamin F. Cravatt","doi":"10.1038/s41557-024-01601-1","DOIUrl":"https://doi.org/10.1038/s41557-024-01601-1","url":null,"abstract":"<p>Covalent chemistry is a versatile approach for expanding the ligandability of the human proteome. Activity-based protein profiling (ABPP) can infer the specific residues modified by electrophilic compounds through competition with broadly reactive probes. However, the extent to which such residue-directed platforms fully assess the protein targets of electrophilic compounds in cells remains unclear. Here we evaluate a complementary protein-directed ABPP method that identifies proteins showing stereoselective reactivity with alkynylated, chiral electrophilic compounds—termed stereoprobes. Integration of protein- and cysteine-directed data from cancer cells treated with tryptoline acrylamide stereoprobes revealed generally well-correlated ligandability maps and highlighted features, such as protein size and the proteotypicity of cysteine-containing peptides, that explain gaps in each ABPP platform. In total, we identified stereoprobe binding events for >300 structurally and functionally diverse proteins, including compounds that stereoselectively and site-specifically disrupt MAD2L1BP interactions with the spindle assembly checkpoint complex leading to delayed mitotic exit in cancer cells.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":21.8,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141974106","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 : 2024-08-12DOI: 10.1038/s41557-024-01599-6
Kang Sun, Yan Huang, Fusai Sun, Qingyu Wang, Yujie Zhou, Jingxue Wang, Qun Zhang, Xusheng Zheng, Fengtao Fan, Yi Luo, Jun Jiang, Hai-Long Jiang
Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal–organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn2+ nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor–acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting.
{"title":"Dynamic structural twist in metal–organic frameworks enhances solar overall water splitting","authors":"Kang Sun, Yan Huang, Fusai Sun, Qingyu Wang, Yujie Zhou, Jingxue Wang, Qun Zhang, Xusheng Zheng, Fengtao Fan, Yi Luo, Jun Jiang, Hai-Long Jiang","doi":"10.1038/s41557-024-01599-6","DOIUrl":"https://doi.org/10.1038/s41557-024-01599-6","url":null,"abstract":"<p>Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal–organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn<sup>2+</sup> nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor–acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":21.8,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141918788","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 : 2024-08-08DOI: 10.1038/s41557-024-01598-7
Chi Hun 'William' Choi, Jaeho Shin, Lucas Eddy, Victoria Granja, Kevin M Wyss, Bárbara Damasceno, Hua Guo, Guanhui Gao, Yufeng Zhao, C Fred Higgs, Yimo Han, James M Tour
Sustainable manufacturing that prioritizes energy efficiency, minimal water use, scalability and the ability to generate diverse materials is essential to advance inorganic materials production while maintaining environmental consciousness. However, current manufacturing practices are not yet equipped to fully meet these requirements. Here we describe a flash-within-flash Joule heating (FWF) technique-a non-equilibrium, ultrafast heat conduction method-to prepare ten transition metal dichalcogenides, three group XIV dichalcogenides and nine non-transition metal dichalcogenide materials, each in under 5 s while in ambient conditions. FWF achieves enormous advantages in facile gram scalability and in sustainable manufacturing criteria when compared with other synthesis methods. Also, FWF allows the production of phase-selective and single-crystalline bulk powders, a phenomenon rarely observed by any other synthesis method. Furthermore, FWF MoSe2 outperformed commercially available MoSe2 in tribology, showcasing the quality of FWF materials. The capability for atom substitution and doping further highlights the versatility of FWF as a general bulk inorganic materials synthesis protocol.
{"title":"Flash-within-flash synthesis of gram-scale solid-state materials.","authors":"Chi Hun 'William' Choi, Jaeho Shin, Lucas Eddy, Victoria Granja, Kevin M Wyss, Bárbara Damasceno, Hua Guo, Guanhui Gao, Yufeng Zhao, C Fred Higgs, Yimo Han, James M Tour","doi":"10.1038/s41557-024-01598-7","DOIUrl":"https://doi.org/10.1038/s41557-024-01598-7","url":null,"abstract":"<p><p>Sustainable manufacturing that prioritizes energy efficiency, minimal water use, scalability and the ability to generate diverse materials is essential to advance inorganic materials production while maintaining environmental consciousness. However, current manufacturing practices are not yet equipped to fully meet these requirements. Here we describe a flash-within-flash Joule heating (FWF) technique-a non-equilibrium, ultrafast heat conduction method-to prepare ten transition metal dichalcogenides, three group XIV dichalcogenides and nine non-transition metal dichalcogenide materials, each in under 5 s while in ambient conditions. FWF achieves enormous advantages in facile gram scalability and in sustainable manufacturing criteria when compared with other synthesis methods. Also, FWF allows the production of phase-selective and single-crystalline bulk powders, a phenomenon rarely observed by any other synthesis method. Furthermore, FWF MoSe<sub>2</sub> outperformed commercially available MoSe<sub>2</sub> in tribology, showcasing the quality of FWF materials. The capability for atom substitution and doping further highlights the versatility of FWF as a general bulk inorganic materials synthesis protocol.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141907080","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 : 2024-08-08DOI: 10.1038/s41557-024-01606-w
Pokhraj Ghosh, Timothy H. Warren
Nitric oxide is at the heart of myriad environmental and biological processes. Pokhraj Ghosh and Timothy Warren explore the molecular interconnections and wide-ranging impacts of this molecule which is critical for the health of our planet.
{"title":"Get to Know NO","authors":"Pokhraj Ghosh, Timothy H. Warren","doi":"10.1038/s41557-024-01606-w","DOIUrl":"10.1038/s41557-024-01606-w","url":null,"abstract":"Nitric oxide is at the heart of myriad environmental and biological processes. Pokhraj Ghosh and Timothy Warren explore the molecular interconnections and wide-ranging impacts of this molecule which is critical for the health of our planet.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141907081","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 : 2024-08-08DOI: 10.1038/s41557-024-01602-0
Bruce C. Gibb
In his previous Thesis, Bruce Gibb introduced us to the chemistry of Jupiter’s moons. Now, he takes us on a tour of NASA’s Europa Clipper, the spacefaring chemistry lab set to revolutionize our understanding of Jupiter’s most intriguing satellite.
{"title":"How to search for Europan life","authors":"Bruce C. Gibb","doi":"10.1038/s41557-024-01602-0","DOIUrl":"10.1038/s41557-024-01602-0","url":null,"abstract":"In his previous Thesis, Bruce Gibb introduced us to the chemistry of Jupiter’s moons. Now, he takes us on a tour of NASA’s Europa Clipper, the spacefaring chemistry lab set to revolutionize our understanding of Jupiter’s most intriguing satellite.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141907082","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 : 2024-08-05DOI: 10.1038/s41557-024-01597-8
Ze-Jie Lv, Kim A Eisenlohr, Robert Naumann, Thomas Reuter, Hendrik Verplancke, Serhiy Demeshko, Regine Herbst-Irmer, Katja Heinze, Max C Holthausen, Sven Schneider
The extraordinary advances in carbene (R1-C-R2) chemistry have been fuelled by strategies to stabilize the electronic singlet state via π interactions. In contrast, the lack of similarly efficient approaches to obtain authentic triplet carbenes with appreciable lifetimes beyond cryogenic temperatures hampers their exploitation in synthesis and catalysis. Transition-metal substitution represents a potential strategy, but metallocarbenes (M-C-R) usually represent high-lying excited electronic configurations of the well-established carbyne complexes (M≡C-R). Here we report the synthesis and characterization of triplet metallocarbenes (M-C-SiMe3, M = PdII, PtII) that are persistent beyond cryogenic conditions, and their selective reactivity towards carbene C-H insertion and carbonylation. Bond analysis reveals significant stabilization by spin-polarized push-pull interactions along both π-bonding planes, which fundamentally differs from bonding in push-pull singlet carbenes. This bonding model, thus, expands key strategies for stabilizing the open-shell carbene electromers and closes a conceptual gap towards carbyne complexes.
{"title":"Triplet carbenes with transition-metal substituents.","authors":"Ze-Jie Lv, Kim A Eisenlohr, Robert Naumann, Thomas Reuter, Hendrik Verplancke, Serhiy Demeshko, Regine Herbst-Irmer, Katja Heinze, Max C Holthausen, Sven Schneider","doi":"10.1038/s41557-024-01597-8","DOIUrl":"https://doi.org/10.1038/s41557-024-01597-8","url":null,"abstract":"<p><p>The extraordinary advances in carbene (R<sup>1</sup>-C-R<sup>2</sup>) chemistry have been fuelled by strategies to stabilize the electronic singlet state via π interactions. In contrast, the lack of similarly efficient approaches to obtain authentic triplet carbenes with appreciable lifetimes beyond cryogenic temperatures hampers their exploitation in synthesis and catalysis. Transition-metal substitution represents a potential strategy, but metallocarbenes (M-C-R) usually represent high-lying excited electronic configurations of the well-established carbyne complexes (M≡C-R). Here we report the synthesis and characterization of triplet metallocarbenes (M-C-SiMe<sub>3</sub>, M = Pd<sup>II</sup>, Pt<sup>II</sup>) that are persistent beyond cryogenic conditions, and their selective reactivity towards carbene C-H insertion and carbonylation. Bond analysis reveals significant stabilization by spin-polarized push-pull interactions along both π-bonding planes, which fundamentally differs from bonding in push-pull singlet carbenes. This bonding model, thus, expands key strategies for stabilizing the open-shell carbene electromers and closes a conceptual gap towards carbyne complexes.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141893817","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 : 2024-08-05DOI: 10.1038/s41557-024-01594-x
Roberto Nolla-Saltiel, Zachary T. Ariki, Stefanie Schiele, Jana Alpin, Yasuyo Tahara, Daisuke Yokogawa, Masakazu Nambo, Cathleen M. Crudden
Methods to form carbon–carbon bonds efficiently and with control of stereochemistry are critical for the construction of complex molecules. Cross-coupling reactions are among the most efficient and widely used reactions to construct molecules, with reactions enabling the retention or installation of chirality as recent additions to this powerful toolbox. Sulfones are robust, accessible organic electrophiles that have many attractive features as cross-coupling partners; however, since the first example of their use in 1979, there have been no examples of their use in enantioselective, enantiospecific or entantioconvergent cross-couplings. The high acidity of sulfones makes it unclear whether this transformation is even possible outside tertiary systems. Here we report the enantiospecific cross-coupling of cyclic sulfones and Grignard reagents. Up to 99% chirality transfer is observed despite the strong basicity of the Grignard components. In situ monitoring reveals that the cross-coupling is kinetically competitive with competing deprotonation, resulting in a highly enantioselective transformation. Cross-coupling reactions are among the most important carbon–carbon bond-forming reactions. Now the nickel-catalysed cross-coupling of chiral sulfones with Grignard reagents has been achieved with up to 99% retention of chirality. The speed of the cross-coupling relative to sulfone deprotonation and racemization is critical to enabling this enantiospecific process.
{"title":"Enantiospecific cross-coupling of cyclic alkyl sulfones","authors":"Roberto Nolla-Saltiel, Zachary T. Ariki, Stefanie Schiele, Jana Alpin, Yasuyo Tahara, Daisuke Yokogawa, Masakazu Nambo, Cathleen M. Crudden","doi":"10.1038/s41557-024-01594-x","DOIUrl":"10.1038/s41557-024-01594-x","url":null,"abstract":"Methods to form carbon–carbon bonds efficiently and with control of stereochemistry are critical for the construction of complex molecules. Cross-coupling reactions are among the most efficient and widely used reactions to construct molecules, with reactions enabling the retention or installation of chirality as recent additions to this powerful toolbox. Sulfones are robust, accessible organic electrophiles that have many attractive features as cross-coupling partners; however, since the first example of their use in 1979, there have been no examples of their use in enantioselective, enantiospecific or entantioconvergent cross-couplings. The high acidity of sulfones makes it unclear whether this transformation is even possible outside tertiary systems. Here we report the enantiospecific cross-coupling of cyclic sulfones and Grignard reagents. Up to 99% chirality transfer is observed despite the strong basicity of the Grignard components. In situ monitoring reveals that the cross-coupling is kinetically competitive with competing deprotonation, resulting in a highly enantioselective transformation. Cross-coupling reactions are among the most important carbon–carbon bond-forming reactions. Now the nickel-catalysed cross-coupling of chiral sulfones with Grignard reagents has been achieved with up to 99% retention of chirality. The speed of the cross-coupling relative to sulfone deprotonation and racemization is critical to enabling this enantiospecific process.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":null,"pages":null},"PeriodicalIF":19.2,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141893816","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}