Nature synthesis最新文献_第8页

Phase engineering of nitride thin films 氮化薄膜的相位工程

Nature synthesis Pub Date : 2024-09-30 DOI: 10.1038/s44160-024-00666-7

Xing Ming, Xiaojun Kuang

引用次数: 0

Carbon isotopic labelling of carboxylic acids enabled by organic photoredox-catalysed cyanation 有机光氧化催化氰化作用下羧酸的碳同位素标记

Nature synthesis Pub Date : 2024-09-27 DOI: 10.1038/s44160-024-00656-9

Zhengbo Zhu, Xuedan Wu, Gerald Thomas Bida, Huaifu Deng, Xinrui Ma, Siran Qian, Zhanhong Wu, Zibo Li, David A. Nicewicz

{"title":"Carbon isotopic labelling of carboxylic acids enabled by organic photoredox-catalysed cyanation","authors":"Zhengbo Zhu, Xuedan Wu, Gerald Thomas Bida, Huaifu Deng, Xinrui Ma, Siran Qian, Zhanhong Wu, Zibo Li, David A. Nicewicz","doi":"10.1038/s44160-024-00656-9","DOIUrl":"10.1038/s44160-024-00656-9","url":null,"abstract":"The application of molecular imaging has advanced personalized medicine and generated a profound impact on patient care. Positron emission tomography and magnetic resonance imaging are among the most widely used imaging modalities, often requiring the isotopic labelling of bioactive molecules to generate the desired imaging probes. Unfortunately, radiochemistry often limits the development of novel agents due to complicated syntheses and the incompatibility of complex molecules. Here, considering the prevalence of carboxylic acids in drug and bioactive molecules, we have developed a method to perform 11/13C labelling through carboxylic acid groups via organic photoredox reactions to generate radiolabelled nitriles. We applied this strategy to a range of aliphatic carboxylic acids, including complex and functionalized drug molecules, amino acids and short peptides. Notably, when benzylic and alkyl carboxylic acids were used as substrates, a copper co-catalyst was required to obtain the labelled nitriles, whereas when α-amino acids and peptides were used as substrates, a copper co-catalyst was not required to form labelled α-amino nitriles. The radiolabelled nitrile products could be easily converted back to radiolabelled carboxylic acids with high radiochemical yields and molar activities. Positron emission tomography and magnetic resonance imaging are two powerful imaging modalities that require the installation of isotopes in biologically relevant molecules. Now an organic photoredox-catalysed method for the conversion of a range of carboxylic acids to their 11C and 13C isotopomers via decarboxylative cyanation is reported.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"97-105"},"PeriodicalIF":0.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995920","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

Palladium-catalysed [2σ + 2π] cycloaddition reactions of bicyclo[1.1.0]butanes with aldehydes 钯催化双环[1.1.0]丁烷与醛的[2σ + 2π]环加成反应

Nature synthesis Pub Date : 2024-09-27 DOI: 10.1038/s44160-024-00659-6

Tianzhu Qin, Mengyang He, Weiwei Zi

{"title":"Palladium-catalysed [2σ + 2π] cycloaddition reactions of bicyclo[1.1.0]butanes with aldehydes","authors":"Tianzhu Qin, Mengyang He, Weiwei Zi","doi":"10.1038/s44160-024-00659-6","DOIUrl":"10.1038/s44160-024-00659-6","url":null,"abstract":"Cycloaddition reactions of bicyclo[1.1.0]butanes (BCBs) with 2π components are a powerful tool for preparing C(sp3)-rich arene bioisosteres. Despite enormous progress in this field, catalytic enantioselective cycloadditions of BCBs that produce enantioenriched three-dimensional bioisosteres are underdeveloped. Here we report a palladium-catalysed [3 + 2] cycloaddition reaction of vinyl-carbonyl-BCBs with carbonyl compounds, including formaldehyde, activated ketones, and aliphatic and aromatic aldehydes. This approach provides quick access to a wide variety of 2-oxabicyclo[2.1.1]hexanes. Density functional theory calculations indicate that the reaction occurs through a zwitterionic mechanism involving σ-bond cleavage, nucleophilic addition and allylic substitution. When (R,R)-ANDEN-phenyl Trost ligand is used, the stereoselectivity of the addition of palladium-zwitterionic enolates to carbonyl can be controlled to achieve enantioselective [3 + 2] cycloadditions. We further demonstrate the practicality of the method by carrying out several downstream transformations of cycloaddition products. Palladium catalysis enables the cycloaddition reaction between vinyl-carbonyl-bicyclo[1.1.0]butanes and aldehydes or ketones for the synthesis of 2-oxabicyclo[2.1.1]hexanes, an arene bioisotere. Enantiocontrol over the zwitterionic [2σ + 2π] cycloaddition process can be achieved using the commercially available (R,R)-ANDEN-phenyl Trost ligand.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 1","pages":"124-133"},"PeriodicalIF":0.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995868","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

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