Nature chemistry最新文献_第7页

On-support phosphitylation for oligonucleotide modification 支持磷酸化寡核苷酸修饰。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-27 DOI: 10.1038/s41557-026-02229-z

引用次数: 0

Highly chemoselective access to alkyl-sulfur compounds via N2 extrusion of alkyl hydrazines 通过氮气挤压烷基肼获得烷基硫化合物的高度化学选择性。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-22 DOI: 10.1038/s41557-026-02212-8

Shuanghu Wang, David A. Cagan, Jet Tsien, Jiapei Zhang, Thirupathi Gogula, Appala Venkata Ramana Murthy, Sampath Kumar Nangunoori, Gohith Boga, Martins S. Oderinde, Adrianna M. Turner, Howard C. Hang, Yu Kawamata, Phil S. Baran

{"title":"Highly chemoselective access to alkyl-sulfur compounds via N2 extrusion of alkyl hydrazines","authors":"Shuanghu Wang, David A. Cagan, Jet Tsien, Jiapei Zhang, Thirupathi Gogula, Appala Venkata Ramana Murthy, Sampath Kumar Nangunoori, Gohith Boga, Martins S. Oderinde, Adrianna M. Turner, Howard C. Hang, Yu Kawamata, Phil S. Baran","doi":"10.1038/s41557-026-02212-8","DOIUrl":"10.1038/s41557-026-02212-8","url":null,"abstract":"Sulfur(VI)-containing functional groups, such as sulfonamides, sulfinates and sulfonyl fluorides, are ubiquitous in pharmaceuticals, where they confer unique physicochemical properties that enhance metabolic stability, solubility and bioactivity across diverse therapeutic areas. Despite their prevalence, synthetic access to alkyl-sulfur(VI) derivatives remains fragmented, often requiring multi-step sequences from scarce precursors or harsh conditions that limit functional-group tolerance and scalability. Here we report a unified platform that enables divergent synthesis of alkyl-sulfur(VI) compounds from abundant, unactivated feedstocks including ketones, alcohols, amines and other structurally complex molecules. Central to this method is the use of alkyl hydrazines (or their sulfonylated derivatives) as practical radical precursors. Upon simple thermal activation, these hydrazines undergo efficient homolysis to generate alkyl radicals under mild and operationally simple conditions, without the need for photocatalysts, expensive metals or reagents and elaborate setups. Over 70 sulfur-containing molecules are synthesized, including direct functionalization of complex natural products without resorting to protecting group chemistry. A unified platform for divergent synthesis of alkyl-sulfur(VI) compounds is reported using alkyl hydrazines and hydrazides as practical radical precursors. Upon simple thermal activation, these readily accessible precursors undergo N2 extrusion to generate alkyl radicals under mild conditions, enabling chemoselective access to complex, functionality-rich sulfinates, sulfonyl fluorides and sulfinamides.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 10","pages":"1790-1799"},"PeriodicalIF":24.5,"publicationDate":"2026-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148562408","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}

引用次数: 0

Aggregation affords productive photocatalysis 聚合提供生产性光催化。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-22 DOI: 10.1038/s41557-026-02217-3

Xueliang Shi, Hai-Bo Yang

引用次数: 0

A versatile strategy for oligonucleotide functionalization via on-support phosphitylation 通过支持磷酸化实现寡核苷酸功能化的通用策略。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-22 DOI: 10.1038/s41557-026-02214-6

Ayan Dasgupta, Sebastian Golojuch, Li Xiao, Nour Eddine Fahmi, Edward A. Anderson, Tom Brown

{"title":"A versatile strategy for oligonucleotide functionalization via on-support phosphitylation","authors":"Ayan Dasgupta, Sebastian Golojuch, Li Xiao, Nour Eddine Fahmi, Edward A. Anderson, Tom Brown","doi":"10.1038/s41557-026-02214-6","DOIUrl":"10.1038/s41557-026-02214-6","url":null,"abstract":"Chemically modified nucleic acids such as antisense oligonucleotides, small interfering RNA and CRISPR guide RNA have emerged as transformative modalities in modern medicine, providing new strategies for the treatment of genetic and metabolic disorders, viral infections and cancer. However, their application is limited by challenges related to intracellular delivery and targeting, advances in which would benefit from a broader range of methods for chemical functionalization. Here we describe a streamlined approach using inexpensive, bench-stable alcohols or nucleosides that enables site-selective modification at the 5′ and 3′ termini and at internal sites of synthetic oligonucleotides. Our strategy offers a conceptually straightforward solution to this problem through the in situ generation of phosphoramidites on the solid-supported oligonucleotide. The methodology displays high coupling efficiency, high functional-group compatibility with azides, amines and thiols, and efficient recovery of excess alcohols/monomers, thus offering a robust platform for advancing and diversifying therapeutic oligonucleotide modification. Oligonucleotide modification largely relies on unstable, expensive phosphoramidite reagents, limiting the diversity and efficiency of chemical functionalization. Now, a site-selective modification of synthetic oligonucleotides is reported via the in situ generation of phosphoramidites on the solid-supported oligonucleotide. This approach enables cost-effective and versatile modification of oligonucleotides, including terminal and internal modifications.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 10","pages":"1747-1754"},"PeriodicalIF":24.5,"publicationDate":"2026-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-026-02214-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148552655","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}

引用次数: 0

A photogenerated triplet aura-nitrene for gold-mediated nitrene transfer 一种用于金介导的亚硝基转移的光生三态aura-nitrene。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-21 DOI: 10.1038/s41557-026-02152-3

Jaime Martín, Marc Fernández-Sabaté, Bernhard Spingler, John H. Beale, Dominik Munz, Cristina Nevado

{"title":"A photogenerated triplet aura-nitrene for gold-mediated nitrene transfer","authors":"Jaime Martín, Marc Fernández-Sabaté, Bernhard Spingler, John H. Beale, Dominik Munz, Cristina Nevado","doi":"10.1038/s41557-026-02152-3","DOIUrl":"10.1038/s41557-026-02152-3","url":null,"abstract":"The isolation and characterization of metal-stabilized, low-valent nitrogen species remain central challenges in advancing nitrogen-atom transfer chemistry. Although gold has emerged as a powerful catalyst in C–N bond formation, proposed mechanisms have consistently bypassed gold nitrenes as key intermediates—leaving their chemistry largely uncharted. Here we report the characterization of a bona fide aura-nitrene, formed via photochemical N2 extrusion from a gold(III) azide complex. In crystallo and solid-state analyses reveal a diverse reactivity landscape, including a nitrene-to-nitro transformation via O2 activation, intra- and intermolecular C–H bond activation, CO fixation and alkyne addition/sigmatropic rearrangement. Computational investigations confirm a triplet ground state, with the nitrene best described as a nitrogen-centred diradical σ-bonded to a formal gold(III) centre. These findings highlight the dual electrophilic and diradical character of gold(III) metallonitrenes and establish a conceptual framework for gold-mediated nitrogen-atom transfer beyond conventional mechanistic paradigms. Metal-stabilized nitrenes are important intermediates in nitrogen-atom transfer chemistry, but their isolation is challenging. Now a formal gold(III) aura-nitrene with triplet diradical character has been generated through photoirradiation of an azide precursor. The resulting nitrene enables a range of reactions, including O2 activation and C–H functionalization.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 8","pages":"1413-1421"},"PeriodicalIF":24.5,"publicationDate":"2026-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-026-02152-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148549754","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}

引用次数: 0

A gold nitrene for nitrogen-atom transfer chemistry 用于氮原子转移化学的金腈。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-21 DOI: 10.1038/s41557-026-02216-4

引用次数: 0

A modifying touch for metal–organic framework glasses 金属有机框架眼镜的修饰触摸。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-20 DOI: 10.1038/s41557-026-02207-5

Søren S. Sørensen, Morten M. Smedskjaer

引用次数: 0

Ladder-shaped molecules for the masses 梯子状的分子代表大众。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-20 DOI: 10.1038/s41557-026-02211-9

John A. Milligan, Robert J. Monroe

引用次数: 0

A molecular model for the Ge(100) buckled dimer Ge（100）弯曲二聚体的分子模型

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-14 DOI: 10.1038/s41557-026-02208-4

Paul Janßen, Hannah Szabo, Eva A. M. Roesky, Manuel Schmitt, Fabian Ebner, Lutz Greb

{"title":"A molecular model for the Ge(100) buckled dimer","authors":"Paul Janßen, Hannah Szabo, Eva A. M. Roesky, Manuel Schmitt, Fabian Ebner, Lutz Greb","doi":"10.1038/s41557-026-02208-4","DOIUrl":"10.1038/s41557-026-02208-4","url":null,"abstract":"The ‘buckled dimer’ defines the key properties of silicon and germanium(100) semiconductor surfaces and governs their behaviour during passivation, functionalization and device fabrication. Each dimer combines a Lewis-acidic ‘down’ atom with a Lewis-basic ‘up’ atom, creating a polarized motif that is difficult to isolate or to quantify. Accordingly, their atomically resolved chemistry remains challenging to interrogate. Here we show that structural constraint can translate this surface motif into a molecular system. A calix[4]pyrrolato ligand enforces a unique cis-bent geometry in a dinuclear Ge(II) complex, generating a polarized Ge–Ge unit that emulates the ambiphilic character of a Ge(100) buckled dimer. Structural analysis, quantitative Lewis acidity/basicity measurements and solution-phase reactivity reveal pronounced surface-like features, but clear divergence from conventional digermenes. The rigid geometry creates spatially separated, exceptionally strong Lewis acidic and basic sites that govern distinct reactivity patterns. Accordingly, this work establishes constrained main-group complexes as molecular surrogates for interrogating solid–vacuum interface chemistry in solution. Pairs of surface atoms displaced above and below the surface plane, known as buckled dimers, govern the reactivity of Si and Ge(100) surfaces, but their chemistry at the atomic scale is difficult to isolate and quantify. Now a structurally constraining macrocyclic ligand has enabled the synthesis of a molecular digermene analogue, providing a platform for probing its ambiphilic reactivity in solution.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 10","pages":"1781-1789"},"PeriodicalIF":24.5,"publicationDate":"2026-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148432556","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}

引用次数: 0

Programmable arene ring opening unlocks the diversification of phenols 可编程芳烃环打开解锁酚的多样化

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-07-14 DOI: 10.1038/s41557-026-02204-8

Yilei Huang, Han Zhu, Yichi Chen, Teng Wang, Zhibin Hu, Ming-Hui Zhu, Zengrui Cheng, Hongwei Shi, Junhong Meng, Xi Wang, Yixian Wu, Ning Jiao

{"title":"Programmable arene ring opening unlocks the diversification of phenols","authors":"Yilei Huang, Han Zhu, Yichi Chen, Teng Wang, Zhibin Hu, Ming-Hui Zhu, Zengrui Cheng, Hongwei Shi, Junhong Meng, Xi Wang, Yixian Wu, Ning Jiao","doi":"10.1038/s41557-026-02204-8","DOIUrl":"10.1038/s41557-026-02204-8","url":null,"abstract":"The inert carbon–carbon bonds of aromatic systems have long impeded the direct diversification of phenolic feedstocks into value-added scaffolds. Although enzymatic or energy-intensive strategies enable limited arene modifications, the controlled and programmable ring opening of phenols to unlock both skeletal and functional group diversity remains a fundamental challenge. Here we report an operationally simple and efficient nitrogenation strategy for cleaving phenolic arene rings, converting phenols into uniquely structured acyclic N-containing products including cyanopenta-dienoates, cyanopenta-dienamides and cyanopenta-dienoic acids. The method also enables scaffold hopping of corresponding arene rings, leading to important five-, six- and seven-membered N-heterocycles. The strategy demonstrates broad utility in late-stage modification of bioactive molecules, diversified skeletal remodelling of phenolic feedstocks, and the application of ring-opening products in polymer development. This approach transforms phenols into programmable linchpins for accessing underexplored chemical space, offering broad potential for synthetic chemistry and materials science. Although phenols are abundant and widely useful synthetic feedstocks, selective remodelling of their aromatic skeletons remains elusive, limiting access to broad regions of chemical space. Now it has been shown that a programmable nitrogenative arene ring-opening methodology enables phenol diversification, forming valuable N-functionalized scaffolds for both synthetic chemistry and polymer materials.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 9","pages":"1593-1601"},"PeriodicalIF":24.5,"publicationDate":"2026-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148432559","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}

引用次数: 0