Nature synthesis最新文献_第7页

Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy 通过正规[3 + 3]环加成策略合成杂六苯并硼酸盐

Nature synthesis Pub Date : 2024-07-10 DOI: 10.1038/s44160-024-00595-5

Xinjiang Zhang, Donglin Li, Cheryl Cai Hui Tan, Fiona Hanindita, Yosuke Hamamoto, Adam S. Foster, Shigeki Kawai, Shingo Ito

{"title":"Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy","authors":"Xinjiang Zhang, Donglin Li, Cheryl Cai Hui Tan, Fiona Hanindita, Yosuke Hamamoto, Adam S. Foster, Shigeki Kawai, Shingo Ito","doi":"10.1038/s44160-024-00595-5","DOIUrl":"10.1038/s44160-024-00595-5","url":null,"abstract":"Heteroatom-embedded hexa-peri-hexabenzocoronene (HBC) molecules exhibit interesting properties depending on the number and position of the introduced heteroatoms and are promising materials for applications in organic electronics and supramolecular chemistry. However, their synthesis is quite limited because of the difficulty in selectively introducing heteroatoms into the HBC core, which poses a challenge in organic synthesis. Here we report a strategy for the in-solution synthesis of 3a2-azahexa-peri-hexabenzocoronenium salts, which are cationic nitrogen-embedded HBC derivatives. The synthesis was enabled by the formal [3 + 3] cycloaddition of polycyclic aromatic azomethine ylides with cyclopropenes, as a three-atom dipolarophile, followed by mechanochemical intramolecular cyclization. Furthermore, on-surface polymerization of aza-HBC precursors was performed to synthesize aza-HBC-based chevron-like graphene nanoribbons. This study provides the possibility for the further use of nitrogen-embedded HBC derivatives in a variety of potential applications. Heteroatom-embedded hexa-peri-hexabenzocoronenes (HBCs) display notable properties, but the selective incorporation of heteroatoms into the HBC core makes their synthesis difficult. Now a two-step process for the synthesis of 3a2-azahexabenzocoronenium salts is reported. The process comprises a formal [3 + 3] cycloaddition between azomethine ylides and cyclopropenes, followed by mechanochemical cyclization.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1283-1291"},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141574643","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

Electrosynthesis of urea by using Fe2O3 nanoparticles encapsulated in a conductive metal–organic framework 利用封装在导电金属有机框架中的 Fe2O3 纳米粒子电合成尿素

Nature synthesis Pub Date : 2024-07-10 DOI: 10.1038/s44160-024-00603-8

Da-Shuai Huang, Xiao-Feng Qiu, Jia-Run Huang, Min Mao, Lingmei Liu, Yu Han, Zhen-Hua Zhao, Pei-Qin Liao, Xiao-Ming Chen

{"title":"Electrosynthesis of urea by using Fe2O3 nanoparticles encapsulated in a conductive metal–organic framework","authors":"Da-Shuai Huang, Xiao-Feng Qiu, Jia-Run Huang, Min Mao, Lingmei Liu, Yu Han, Zhen-Hua Zhao, Pei-Qin Liao, Xiao-Ming Chen","doi":"10.1038/s44160-024-00603-8","DOIUrl":"10.1038/s44160-024-00603-8","url":null,"abstract":"The synthesis of urea by the electrochemical co-reduction of CO2 and nitrate is a crucial and challenging task. Catalysts typically suffer from either low Faradaic efficiency (FE) or inadequate current density, leading to a restricted yield rate of urea. Here we report ultrasmall γ-Fe2O3 nanoparticles (<2 nm) encapsulated in the pores of a conductive (40 S cm−1) metal–organic framework Ni-HITP (HITP = 2,3,6,7,10,11-hexaaminotriphenylene), resulting in a composite material, γ-Fe2O3@Ni-HITP. Under neutral conditions, γ-Fe2O3@Ni-HITP exhibited a state-of-art electrocatalytic performance for urea synthesis through the co-reduction of CO2 and nitrate in CO2-saturated 1 M KHCO3 and 0.1 M KNO3 aqueous solutions, achieving a FEurea of 67.2(6)%, a current density of −90 mA cm−2 and an high yield rate of $$20.4(2),{mathrm{g}},{mathrm{h}}^{-1},{mathrm{g}}_{mathrm{cat}}^{-1}$$ (7.7(1) mg h−1 cm−2), which is about five times higher than the rates of previously reported catalysts. No degradation was observed over 150 h of continuous operation at such a high yield rate. Enlarging the electrode area by 125 times yielded about 1.05(4) g of high-purity urea over 8 h. A mechanistic study revealed that Fe(III) ions in the γ-Fe2O3 nanoparticles exhibit high activity, generating the key intermediates *NH2 and *COOH. Furthermore, pairs of adjacent Fe(III) ions in the γ-Fe2O3 nanoparticles can act as highly active catalytic sites for catalysing the C–N coupling between *NH2 and *COOH, resulting in the formation of the subsequent key intermediate *CONH2, thereby contributing to the exceptionally high performance of γ-Fe2O3@Ni-HITP for urea production. Small γ-Fe2O3 nanoparticles (<2 nm) encapsulated in the pores of a conductive metal–organic framework enable the efficient electrosynthesis of urea through the co-reduction of CO2 and nitrate under neutral conditions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 11","pages":"1404-1413"},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141574642","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

Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis 通过钴催化克服杂原子限制的对映选择性烯烃氢烷基化反应

Nature synthesis Pub Date : 2024-07-10 DOI: 10.1038/s44160-024-00581-x

Yan Li, Deguang Liu, Xiao Hu, Jun-Yang Zhang, Qing-Wei Zhu, Boru Men, Gen-Wei Gao, Pei-Wen Chen, Yi-Zhou Tong, Zhe Chang, Zhen Li, Xi Lu, Yao Fu

{"title":"Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis","authors":"Yan Li, Deguang Liu, Xiao Hu, Jun-Yang Zhang, Qing-Wei Zhu, Boru Men, Gen-Wei Gao, Pei-Wen Chen, Yi-Zhou Tong, Zhe Chang, Zhen Li, Xi Lu, Yao Fu","doi":"10.1038/s44160-024-00581-x","DOIUrl":"10.1038/s44160-024-00581-x","url":null,"abstract":"Alkene hydroalkylation enables efficient and selective formation of C(sp3)–C(sp3) bonds with unique advantages, such as exceptional chemoselectivity and remarkable tolerance of functional groups. However, eliminating the heteroatom-containing substrate-specific constraints in achieving precise enantioselectivity remains a challenge in alkene hydroalkylation reactions. Here we report the cobalt-hydride-catalysed enantioselective hydroalkylation of 1,1-disubstituted alkenes, enabling the efficient construction of chiral tertiary carbon centres at the benzyl position. The enantioselective control mode does not rely on Lewis basic or polar heteroatom functional groups; instead, an efficient stereochemical control environment is established between substrates and catalysts through weak C–H···π interactions in the alkene hydrometalation step. This work adds a differentiated case to the Giese-type addition reaction and metal-hydride-catalysed alkene hydroalkylation precedents towards breaking substrate-specific constraints in the enantioselective control mode. Eliminating the substrate-specific constraints in alkene hydroalkylation reactions, where heteroatom-containing substrates are often required to achieve enantioselectivity, remains a challenge. Now a cobalt-hydride catalyst is shown to overcome heteroatom constraints through C–H···π interactions between substrates and catalysts, enabling the efficient construction of chiral tertiary carbon centres at the benzyl position.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 9","pages":"1134-1144"},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141574641","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

Iron-catalysed C(sp²)–H activation for aza-annulation with alkynes on extended π-conjugated systems 铁催化 C(sp²)-H活化，在扩展的π-共轭体系上与炔烃进行偶氮annulation反应

Nature synthesis Pub Date : 2024-07-09 DOI: 10.1038/s44160-024-00605-6

Yan Zhang, Shota Fukuma, Rui Shang, Eiichi Nakamura

{"title":"Iron-catalysed C(sp²)–H activation for aza-annulation with alkynes on extended π-conjugated systems","authors":"Yan Zhang, Shota Fukuma, Rui Shang, Eiichi Nakamura","doi":"10.1038/s44160-024-00605-6","DOIUrl":"10.1038/s44160-024-00605-6","url":null,"abstract":"Sustainable C–H activation methods for expanding large π-systems, crucial for electronic materials, continue to pose a challenge due to the metal–π interaction involving bonding and back-bonding. Here we present an iron-catalysed method for aza-annulation π-extension reactions of conjugated carbonyl compounds via oxime ether, employing a sterically bulky trisphosphine ligand to mitigate Fe–π interaction. Inexpensive isobutyl aluminium(III) catecholate serves as a base. These reactions convert readily available substrates, such as quinacridone, pentacenedione and pentacenetetraone, into conjugated skeletons, yielding several narrow-band-emissive molecules, including an actively pursued deep-blue emitter with peak emission at 450 nm and a narrow emission band of 13 nm. The tetrafold C–H activation of pentacenetetraone, with each step achieving an average yield of 95%, underscores the efficacy of iron catalysis in selectively activating C–H bonds on π-extended systems, offering promise for expanding organic electronic materials. Metal–π interactions typically hinder metal-catalysed C–H functionalization reactions involving large π-conjugated systems. Now, an iron-catalysed aza-annulation method, employing a bulky trisphosphine ligand and an aluminium base, proves efficient for large π-extended substrates, holding promise for electronic materials discovery.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 11","pages":"1349-1359"},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141574658","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

Insight into the role of a trans-AT polyketide synthase in the biosynthesis of lankacidin-type natural products 透视反式 AT 多酮合成酶在兰卡苷类天然产物生物合成中的作用

Nature synthesis Pub Date : 2024-07-09 DOI: 10.1038/s44160-024-00599-1

Zhen Peng Mai, Bo Zhang, Zi Xuan Pang, Jing Shi, Zi Fei Xu, Bing-Bing Huang, Shi Ying Ma, Rui Hua Jiao, Zhu-Jun Yao, Ren Xiang Tan, Hui Ming Ge

{"title":"Insight into the role of a trans-AT polyketide synthase in the biosynthesis of lankacidin-type natural products","authors":"Zhen Peng Mai, Bo Zhang, Zi Xuan Pang, Jing Shi, Zi Fei Xu, Bing-Bing Huang, Shi Ying Ma, Rui Hua Jiao, Zhu-Jun Yao, Ren Xiang Tan, Hui Ming Ge","doi":"10.1038/s44160-024-00599-1","DOIUrl":"10.1038/s44160-024-00599-1","url":null,"abstract":"Modular polyketide synthases (type I PKSs) are biosynthetic assembly lines for synthesizing a diverse array of natural products. While most PKSs exhibit a linear module architecture, the PKS system for lankacidin-type natural products contains only five modules but carries out eight rounds of polyketide extension, challenging the collinearity rule. Here we show the distinct domain architecture of the polyketide synthase enzyme, CheC, which is central to chejuenolide biosynthesis. CheC not only dissociates from and interacts with both the preceding and succeeding PKS enzymes, creating two linear modules, but also independently assembles an unconventional module, facilitating multiple rounds of polyketide extension in the biosynthetic process. We also unveiled missing functions of certain redundant and absent domains within PKSs, fully elucidating the polyketide assembly process for lankacidin-like natural products. These findings not only reveal the biosynthetic pathway for lankacidin- and chejuenolin-type natural products but also enrich the diverse functions of PKSs, setting the stage for future rational design of PKSs. In vitro biosynthetic analysis reveals that a single trans-AT polyketide synthase (PKS) module iteratively enables five rounds of polyketide elongation and interacts with both the preceding and succeeding PKS enzymes to produce the 17-membered macrocyclic polyketide chejunolide.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1255-1265"},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141574659","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

Publisher Correction: Boryl radicals facilitate C(sp2)–C(sp3) cross-coupling reactions 出版商更正：硼烷基促进 C（sp2）-C（sp3）交叉偶联反应

Nature synthesis Pub Date : 2024-07-09 DOI: 10.1038/s44160-024-00617-2

Jesus Rodrigalvarez, Ruben Martin

引用次数: 0

Iridium-catalysed synthesis of C,N,N-cyclic azomethine imines enables entry to unexplored nitrogen-rich 3D chemical space 铱催化合成 C,N,N-环氮甲基亚胺，进入未探索的富氮三维化学空间

Nature synthesis Pub Date : 2024-07-09 DOI: 10.1038/s44160-024-00574-w

Yaseen A. Almehmadi, Jack McGeehan, Nandini J. Guzman, Kirsten E. Christensen, Ken Yamazaki, Darren J. Dixon

{"title":"Iridium-catalysed synthesis of C,N,N-cyclic azomethine imines enables entry to unexplored nitrogen-rich 3D chemical space","authors":"Yaseen A. Almehmadi, Jack McGeehan, Nandini J. Guzman, Kirsten E. Christensen, Ken Yamazaki, Darren J. Dixon","doi":"10.1038/s44160-024-00574-w","DOIUrl":"10.1038/s44160-024-00574-w","url":null,"abstract":"Three-dimensional nitrogen-rich bridged ring systems are of great interest in drug discovery owing to their distinctive physicochemical and structural properties. However, synthetic approaches towards N–N-bond-containing bridged heterocycles are often inefficient and require tedious synthetic strategies. Here we delineate an iridium-catalysed reductive approach to such architectures from C,N,N-cyclic hydrazide substrates using IrCl(CO)[P(OPh)3]2 and 1,1,3,3-tetramethyldisiloxane (TMDS), which provided efficient access to the unstabilized and highly reactive C,N,N-cyclic azomethine imine dipoles. These species were stable and isolable in their dimeric form, but, upon dissociation in solution, reacted with a broad range of dipolarophiles in [3 + 2] cycloaddition reactions with high yields and good diastereoselectivities, enabling the direct synthesis of nitrogen-rich sp3-hybridized pyrazoline polycyclic ring systems. Density functional theory calculations were performed to elucidate the origin of the diastereoselectivity of the cycloaddition reaction, and principal moment of inertia (PMI) analysis was conducted to enable visualization of the topological information of the dipolar cycloadducts. Three-dimensional nitrogen-rich bridged systems are of great importance in drug design. Now, a synthetic strategy enabling their preparation from readily available starting materials has been developed. This approach provides access to unstabilized C,N,N-cyclic azomethine imines, which are obtained as bench-stable dimers and undergo [3 + 2] cycloaddition reactions with various dipolarophiles.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 9","pages":"1168-1175"},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00574-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141574645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrogenation streamlines cyclolignan synthesis 氢化可简化环木质素合成

Nature synthesis Pub Date : 2024-07-09 DOI: 10.1038/s44160-024-00592-8

David B. Ryffel, David Sarlah

引用次数: 0

Electrosynthesis of C–X bonds from CO2 从二氧化碳中电合成 C-X 键

Nature synthesis Pub Date : 2024-07-05 DOI: 10.1038/s44160-024-00614-5

引用次数: 0

Synthesizing urea from nitrate contaminants 利用硝酸盐污染物合成尿素

Nature synthesis Pub Date : 2024-07-03 DOI: 10.1038/s44160-024-00610-9

Alison Stoddart

引用次数: 0