Nature synthesis最新文献_第6页

Copper-catalysed synthesis of chiral alkynyl cyclopropanes using enantioconvergent radical cross-coupling of cyclopropyl halides with terminal alkynes 环丙基卤化物与末端炔对映收敛自由基交叉偶联铜催化合成手性炔基环丙烷

Nature synthesis Pub Date : 2024-09-26 DOI: 10.1038/s44160-024-00654-x

Zeng Gao, Lin Liu, Ji-Ren Liu, Wang Wang, Ning-Yuan Yang, Lizhi Tao, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu

{"title":"Copper-catalysed synthesis of chiral alkynyl cyclopropanes using enantioconvergent radical cross-coupling of cyclopropyl halides with terminal alkynes","authors":"Zeng Gao, Lin Liu, Ji-Ren Liu, Wang Wang, Ning-Yuan Yang, Lizhi Tao, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu","doi":"10.1038/s44160-024-00654-x","DOIUrl":"10.1038/s44160-024-00654-x","url":null,"abstract":"Transition-metal-catalysed enantioconvergent cross-coupling reactions of highly reactive alkyl radicals often suffer from reduced chemoselectivity, mainly due to side reactions with closed-shell reactants. A strategy to overcome this challenge has yet to be identified, posing substantial limitations on the synthetic utility of this method. Here we report a method for enantioconvergent radical carbon–carbon cross-coupling of highly reactive cyclopropyl radicals with terminal alkynes, using redox state-tuned copper catalysis, under mild conditions. Key to this method is the use of hard chiral N,N,N-ligands in combination with Cu(II) salts of hard ligands/counterions, which results in elevated concentrations of Cu(II) species and thus enhanced cross-coupling reactions. This protocol not only exhibits a broad substrate scope across a wide range of both racemic cyclopropyl halide and terminal alkyne coupling partners but also provides access to useful yet synthetically challenging enantioenriched cyclopropane building blocks. The synthetic use of highly reactive alkyl radicals typically results in low chemoselectivity due to competing side reactions. Now, a redox-state-tuned copper catalytic method is reported, which enables the enantioconvergent cross-coupling of cyclopropyl radicals and terminal alkynes with high chemo- and stereoselectivity.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"84-96"},"PeriodicalIF":0.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995913","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Kinetically controlled Z-alkene synthesis using iron-catalysed allene dialkylation 用铁催化烯二化反应动力学控制z -烯烃合成

Nature synthesis Pub Date : 2024-09-26 DOI: 10.1038/s44160-024-00658-7

Tong-De Tan, Kai Ze Tee, Xiaohua Luo, Peng-Cheng Qian, Xinglong Zhang, Ming Joo Koh

{"title":"Kinetically controlled Z-alkene synthesis using iron-catalysed allene dialkylation","authors":"Tong-De Tan, Kai Ze Tee, Xiaohua Luo, Peng-Cheng Qian, Xinglong Zhang, Ming Joo Koh","doi":"10.1038/s44160-024-00658-7","DOIUrl":"10.1038/s44160-024-00658-7","url":null,"abstract":"Stereodefined trisubstituted alkenes are key constituents of biologically active molecules and also serve as indispensable substrates for a wide range of stereospecific reactions affording sp3-hybridized skeletons. However, there is a persisting lack of methods that generate the thermodynamically less stable Z-isomers. Here we report an iron-catalysed multicomponent strategy that merges allenes, dialkylzinc compounds and haloalkanes to construct trisubstituted alkenes with excellent control of regioselectivity and Z-selectivity. Selective installation of diverse C(sp3) groups enables access to a broad library of functionalized unsaturated products. The synthetic utility of the method is highlighted through the synthesis of a glucosylceramide synthase inhibitor. Contrary to conventional mechanisms for metal-catalysed allene functionalization, our studies suggest a kinetically controlled pathway involving sequential radical-mediated alkylferration of the less hindered C=C bond and inner-sphere alkylation via reductive elimination. Mechanistic and computational investigations reveal the origins of the stereochemical outcome. Catalytic methods that generate Z-alkenes are rare due to the energetic favourability of the corresponding E-alkenes. Now, a bisphosphine–iron catalyst mediates the multicomponent dialkylation of allenes, using dialkylzinc reagents and alkyl halides, to selectively form functionalized trisubstituted Z-alkenes.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"116-123"},"PeriodicalIF":0.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A gallium(i) compound with variable reactivity 一种具有可变反应性的镓化合物

Nature synthesis Pub Date : 2024-09-20 DOI: 10.1038/s44160-024-00653-y

引用次数: 0

Heterochiral catenanes create robust nanostructures 杂手性链烷产生坚固的纳米结构

Nature synthesis Pub Date : 2024-09-20 DOI: 10.1038/s44160-024-00655-w

Josh Phipps, Shengqian Ma

引用次数: 0

Enhanced hydrogen peroxide photosynthesis in covalent organic frameworks through induced asymmetric electron distribution 通过诱导不对称电子分布增强共价有机框架中的过氧化氢光合作用

Nature synthesis Pub Date : 2024-09-19 DOI: 10.1038/s44160-024-00644-z

Youxing Liu, Lu Li, Zhiyuan Sang, Hao Tan, Na Ye, Chenglong Sun, Zongqiang Sun, Mingchuan Luo, Shaojun Guo

{"title":"Enhanced hydrogen peroxide photosynthesis in covalent organic frameworks through induced asymmetric electron distribution","authors":"Youxing Liu, Lu Li, Zhiyuan Sang, Hao Tan, Na Ye, Chenglong Sun, Zongqiang Sun, Mingchuan Luo, Shaojun Guo","doi":"10.1038/s44160-024-00644-z","DOIUrl":"10.1038/s44160-024-00644-z","url":null,"abstract":"Covalent organic frameworks (COFs) can be used as photocatalysts for the direct photosynthesis of hydrogen peroxide (H2O2) from oxygen, water and sunlight. However, their highly symmetric structure can lead to weak adsorption of O2 and, therefore, unsatisfactory photocatalytic performance. Here we explore the local asymmetric electron distribution induced by Pauli and electron–electron repulsion in COFs to construct localized bonding sites for O2 species, which promotes photocatalytic H2O2 production. Experimental results and theoretical calculations reveal that TAPT–FTPB COFs (where TAPT is 1,3,5-tris-(4-aminophenyl) triazine and FTPB is 5-(5-formylthiophen-2-yl)thiophene-2-carbaldehyde) with an asymmetric electron distribution show strong O2 adsorption interaction and a record-breaking solar-to-chemical conversion efficiency of 1.22% for direct photosynthesis of H2O2 from oxygen and water, which is higher than in the photosynthesis of plants (~0.1%). A flow-type photocatalytic microreactor integrated with TAPT–FTPB COFs exhibits 100% sterilization efficiency for killing bacteria and 97.8% conversion for photocatalytic 2-thiophene methylamine coupling. This work reports a strategy for manipulating the local electron distribution in COFs, opening the door for research on the rational design of high-performance photocatalysis with a local asymmetric electron distribution. Covalent organic frameworks (COFs) are promising photocatalysts for the direct photosynthesis of H2O2, but their symmetric structure can lead to weak O2 adsorption. Now thiophene sulfur atoms are introduced into COFs to induce local asymmetric electron distributions, which enhance the O2 adsorption capacity and interaction of the COFs, promoting direct photosynthesis of H2O2.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"134-141"},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A singly bonded gallanediyl with redox-active and redox-inert reactivity 具有氧化还原活性和氧化还原惰性的单键加兰二基

Nature synthesis Pub Date : 2024-09-19 DOI: 10.1038/s44160-024-00639-w

Simon H. F. Schreiner, Tobias Rüffer, Robert Kretschmer

{"title":"A singly bonded gallanediyl with redox-active and redox-inert reactivity","authors":"Simon H. F. Schreiner, Tobias Rüffer, Robert Kretschmer","doi":"10.1038/s44160-024-00639-w","DOIUrl":"10.1038/s44160-024-00639-w","url":null,"abstract":"Singly bonded metallylenes (R–M:) of the group 13 elements feature a non-bonding pair of electrons together with two vacant orbitals, which makes them highly reactive ambiphiles that readily activate small molecules by oxidative addition. As a consequence of their pronounced reactivity, examples of organometallics with singly bonded aluminium(I) and gallium(I) centres remain rare. Here we report the one-step synthesis of a monomeric gallium(I) compound that readily undergoes oxidative addition reactions and, more remarkably, carbometalation reactions with alkynes by retention of the low +I oxidation state and the singly bonded nature of gallium. This observation contrasts with common reports on the reactivity of low-valent main-group compounds, which are regularly oxidized to compounds in a more stable higher oxidation state. This approach provides access to low-valent main-group compounds and paves the way for the development of bond-functionalization strategies that may enable the discovery of catalytic processes in the future. A singly bonded gallanediyl undergoes carbometalation reactions with alkynes by retaining the low +I oxidation state and the singly bonded nature of gallium. The insertion into the gallium(I)–carbon bond proceeds regioselectively and gives exclusively the syn-addition products.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"67-74"},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142251973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

External forces align supramolecular materials 外力调整超分子材料

Nature synthesis Pub Date : 2024-09-16 DOI: 10.1038/s44160-024-00647-w

Matthew J. Harrington

引用次数: 0

Interfacially coupled Cu-cluster/GaN photocathode for efficient CO2 to ethylene conversion 用于将二氧化碳高效转化为乙烯的簇间耦合铜/氮化镓光电阴极

Nature synthesis Pub Date : 2024-09-12 DOI: 10.1038/s44160-024-00648-9

Bingxing Zhang, Peng Zhou, Zhengwei Ye, Ishtiaque Ahmed Navid, Yuyang Pan, Yixin Xiao, Kai Sun, Zetian Mi

{"title":"Interfacially coupled Cu-cluster/GaN photocathode for efficient CO2 to ethylene conversion","authors":"Bingxing Zhang, Peng Zhou, Zhengwei Ye, Ishtiaque Ahmed Navid, Yuyang Pan, Yixin Xiao, Kai Sun, Zetian Mi","doi":"10.1038/s44160-024-00648-9","DOIUrl":"10.1038/s44160-024-00648-9","url":null,"abstract":"The photoelectrochemical synthesis of valuable multicarbon products from carbon dioxide, sunlight and water is a promising pathway for clean energy generation and carbon neutrality. However, it is challenging to create and stabilize efficient C–C coupling sites to achieve multicarbon products with high selectivity, yield and stability. Here we designed a low-coordinated copper-cluster catalyst interfacially coupled in situ with a GaN nanowire photocathode, achieving a high ethylene Faradaic efficiency of ∼61% and a partial current density of 14.2 mA cm−2, with a robust stability of ∼116 h. The in situ self-optimized Ga–N–O interface was confirmed to facilitate and stabilize the interfacially oxidized copper species of copper clusters, which function as efficient C–C coupling sites for ethylene production. Furthermore, the hydrogen-feeding effect of GaN for promoting CO hydrogenation also guides the facile CHO-involved C–C coupling pathway. This work sheds light on the interface design and understanding of efficient and stable (photo)electrosynthesis of highly valuable fuels from CO2. An interfacially coupled Cu-cluster/GaN photocathode is designed to overcome the efficiency and stability bottlenecks in photoelectrochemical CO2 reduction to multicarbon products. The self-optimized Ga–N–O interface facilitates and stabilizes interfacially oxidized copper species of copper clusters, which function as efficient C–C coupling sites for ethylene production.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 12","pages":"1567-1576"},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Computational analysis of modular diazotransfer reactions for the development of predictive reactivity models and diazotransfer reagents 对模块重氮转移反应进行计算分析，以开发预测性反应模型和重氮转移试剂

Nature synthesis Pub Date : 2024-09-10 DOI: 10.1038/s44160-024-00633-2

Meng-Meng Zheng, Liu Cai, Tiancheng Ma, Hao-Dong Tan, Xiaoyu Lai, Jiajia Dong, Xiao-Song Xue

{"title":"Computational analysis of modular diazotransfer reactions for the development of predictive reactivity models and diazotransfer reagents","authors":"Meng-Meng Zheng, Liu Cai, Tiancheng Ma, Hao-Dong Tan, Xiaoyu Lai, Jiajia Dong, Xiao-Song Xue","doi":"10.1038/s44160-024-00633-2","DOIUrl":"10.1038/s44160-024-00633-2","url":null,"abstract":"The development of the sulfur(VI)–fluoride exchange (SuFEx) and modular diazotransfer (MoDAT) reactions represent important milestones in the evolution of click chemistry. However, their reactivity profiles, chemoselectivity origins and underlying mechanisms remain unclear. Here we report a computational study of the MoDAT and SuFEx pathways, focusing on the reaction between the diazotransfer reagent fluorosulfuryl azide and primary amines. Our calculations reveal that the MoDAT reaction possesses a small kinetic barrier and a strong driving force, making it kinetically and thermodynamically more favourable than the SuFEx reaction. Through mechanistic scrutiny and structure–activity relationship studies, we have formulated predictive models for the reactivity and selectivity of the MoDAT reaction. Leveraging these insights, an easy-to-prepare and easily handled diazotransfer reagent with excellent reactivity has been developed, which holds broad promise for applications in chemistry and biology. Computational analysis of competing sulfur(VI)–fluoride exchange and modular diazotransfer pathways in the reaction between primary amines and fluorosulfuryl azide reveals that diazotransfer is more kinetically and thermodynamically favoured. Predictive models are formulated by combining mechanistic analysis and structure–activity relationship studies, enabling the development of an easy-to-prepare and highly reactive diazotransfer reagent.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 12","pages":"1507-1517"},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Computationally guided design of a diazotransfer reagent with high reactivity 高反应性重氮转移试剂的计算引导设计

Nature synthesis Pub Date : 2024-09-10 DOI: 10.1038/s44160-024-00634-1

引用次数: 0