Article
Chemistry, Inorganic & Nuclear
Inga-Alexandra Bischoff, Ronay Seydo Meme, Muniba Shahzad Bhatti, Bernd Morgenstern, Andre Schaefer
Summary: The synthesis and characterization of bis(indenyl)-tetrelocenophanes of germanium(II), tin(II), and lead(II), which belong to the bis(indenyl)metallocenophane-type species of p-block elements, are reported. The structural characterization of these species in the solid state reveals some unusual features, including a dispersion dimer and an arene complex.
Article
Chemistry, Multidisciplinary
Jiaping Xu, Xin Xu, Danyang Li, Bin-Bin Xie, Jiwen Jian
Summary: Two novel boron heterocyclic radicals, an addition bicyclo[4.2.1]octa-1,3,5-trien-1-yl-borane radical (A) and an insertion 7-1H-borolo[1,2-a]borinine radical (B), were synthesized and characterized in the reaction of atomic boron with benzocyclobutene. Species B involving a fused boron heterocyclic was spectroscopically characterized for the first time. This work is a new approach for boron-mediated molecular editing and the synthesis of fused boron heterocyclic compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Yuto Suga, Yusuke Sunada
Summary: This research focuses on the relationship between an Fe(ii) bromide complex and a six-membered silacycle-bridged biphenyl-based ligand, revealing that the hapticity of the silacycle-based ligand increases from eta 1 to eta 5 upon reduction.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Xiaofeng Liu, Ying Shao, Jiangtao Sun
Summary: A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, providing N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to this unprecedented reaction is the use of CpRu(PPh3)(2)Cl as the catalyst and sulfoxonium ylides as the alkylation reagents, which can also be applied to 7-azaindoles with slight variations in reaction conditions. Furthermore, sulfonium ylides are also suitable alkylation reagents for good selectivity in N-alkylation of 2-pyridones.
Article
Chemistry, Multidisciplinary
Zheng-Chun Yin, Mingjie Li, Chuang Niu, Wei-Feng Wang, Wen-Rui Liu, Qian-Wen Zhang, Guan-Wu Wang
Summary: This study achieves the reductive electrosynthesis of heterocycle-fused fulleroids from fullerotetrahydropyridazines and electrophiles in the presence of a trace amount of oxygen, with concurrent ring contraction and expansion reactions. Depending on the electrophiles used, different regioselective formations of heterocycle-fused fulleroids are achieved. The reaction proceeds through multiple steps, and the structures of the synthesized fulleroids have been determined and their high regioselectivities rationalized by theoretical calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Rebeka Eshagh Saatlo, Jan P. Matiba, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: This paper reports a gold(I)-catalyzed cyclization reaction that directly synthesizes cyclopenta-fused anthracenes (CP-anthracenes) from easily available triene-yne systems with a benzofulvene substructure. These target compounds are of great interest for their potential use as organic materials and the preparation of these compounds is gaining significant importance. The starting materials used in this study are readily available through a three-step synthesis, which further highlights the advantages of this approach. In addition, UV-Vis and fluorescent spectra of the synthesized CP-anthracenes were recorded.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Hue Minh Thi Nguyen, Tran Ngoc Dung, Nguyen Van Trang, Ngo Tuan Cuong, Nguyen Van Minh, Hien Nguyen, Minh Tho Nguyen
Summary: The influence of various substituents on six fused-ring systems designed based on the bithiophene moiety was investigated using quantum chemical computations. Results show that modified molecules with substituents at the alpha-position of fused-ring bithiophene have smaller band gaps and improved electron injection and transport properties compared to the parent compounds.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Simon de Graaff, Marcel Eilers, Julia Buschermoehle, Nina Bengen, Anna Dierks, Marc Schmidtmann, Manfred Manssen, Ruediger Beckhaus
Summary: Complex 1 reacts with methyl lithium to form methylated complex 2 and with lithium 2,6-diisopropylanilide to form imido complex 3. Complex 2 reacts with primary aromatic and aliphatic amines to form niobocene imido complexes and with water to form terminal oxo complex. Complex 3 shows unique reactivity with various substrates, including phenols and nitriles, resulting in the formation of corresponding alkylidene amido and imidato complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Akito Nakai, Tomoki Yoneda, Takayuki Tanaka, Atsuhiro Osuka
Summary: Pd-II complexation induced meso-carbon extrusion of N-fused [22]pentaphyrin(1.1.1.1.1), resulting in the formation of 22 pi aromatic compounds [22]sapphyrin. Oxidation of the compound yielded directly C-N linked dimer.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Ting-Yu Zheng, Yu-Qiang Zhou, Ning Yu, Yu-Lin Li, Tao Wei, Lan Peng, Yu Ling, Kun Jiang, Ye Wei
Summary: In the presence of a copper catalyst, oximes undergo deconstructive insertion into coumarins, resulting in the formation of structurally interesting dihydrobenzofuran-fused pyridones. The reaction yields moderate to good with good functional group compatibility. Investigation of the photoluminescent properties suggests that some of the synthesized compounds may have potential as fluorescent materials.
Article
Chemistry, Organic
Sudarshan Debnath, Mei Lu, Lingli Liang, Yian Shi
Summary: An efficient tandem nucleophilic aminopalladation and carbene insertion sequence is described for the synthesis of indole fused polycycles, providing various substituted indeno[1,2-b]indoles in up to 99% yields.
Article
Multidisciplinary Sciences
Marina Guerrero-Puigdevall, Narcis Fernandez-Fuentes, Jordi Frigola
Summary: This study shows the topological problem of DNA insertion in the stacking of OC with MCM-Cdt1, and the essential role of Cdt1's C-WHD in binding with Mcm6's crucial C-WHD for the latching between MCM-Cdt1 and OC.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Jing Shang, Varsha J. Thombare, Carlie L. Charron, Uta Wille, Craig A. Hutton
Summary: The reaction of thiolactams with N-Boc amino acids promoted by Ag-I results in the formation of N-(alpha-aminoacyl) lactam, which can rearrange through an acyl transfer process. Deprotection of Boc leads to the ring expansion adduct, allowing for the insertion of an amino acid into the thioamide bond to generate medium-sized heterocycles. This method is demonstrated for the site-specific insertion of amino acids into cyclic peptides.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Shengting Xu, Zhongzhi Zhu, Zhendong Yang, Zuyu Mai, Tianxiang Chen, Aijun Ma, Xiuwen Chen
Summary: This study presents a novel method for synthesizing thiazinopyrrole fused ring derivatives using a ring-opening recombination strategy with benzothiazole salts. Thiazolium salts, aldehydes, and amines undergo a cascade cyclization reaction in ethanol solvent conditions, leading to the efficient synthesis of the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Puthannur K. Anjalikrishna, Shridhar R. Gadre, Cherumuttathu H. Suresh
Summary: This study investigates the phenomenon of antiaromaticity-aromaticity interplay in aromatic-antiaromatic fused systems using molecular electrostatic potential (MESP) analysis. The fused systems reduce antiaromaticity by adopting configurations with the least number of localized bonds over antiaromatic moieties, leading to predictions of the most stable configurations. The stability of the fused system is influenced by the empty pi-character of the antiaromatic ring, with the configurations containing the maximum number of 'empty' rings considered the most stable.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Inorganic & Nuclear
Miaomiao Zhu, Tianyu Li, Zhengqi Chai, Junnian Wei, Ze-Jie Lv, Wen-Xiong Zhang
Summary: Reduced arene complexes of rare-earth metals are of great interest due to their unique reactivity, and this study presents the synthesis and structural characterization of these complexes. The rapid inter-ring rearrangement of reduced anthracene complexes of mononuclear scandium is discovered, and a reduced anthracene complex with a scandium center attached to the terminal six-membered ring of anthracene is successfully synthesized. Moreover, the diversified two-electron redox reactions of the reduced naphthalene complex of mononuclear scandium towards various substances are examined, expanding the scope of two-electron redox reactions.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Qingde Zhuo, Xiaoxi Zhou, Takanori Shima, Zhaomin Hou
Summary: This review focuses on N-2 activation and addition to unsaturated substrates mediated by transition metal complexes, which resulted in various N-C bond formation products. The emphasis is on the reaction modes and mechanisms. It is hoped that this work will inspire further explorations in this challenging field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ze-Jie Lv, Wei Liu, Wen-Xiong Zhang
Summary: As key intermediates in metal-promoted/catalyzed C-C bond coupling reactions of nitriles and alkynes, azametallacyclopentadienes, M(N=CR1-CR2=CR3), are an important class of azametallacycles. Research on their solid-state structures, intrinsic reactivity, and synthetic application was limited until the beginning of this century when they were found to have applications in the synthesis of heterocycles. Since then, various complexes with this motif have been isolated and characterized, including rare-earth azametallacyclopentadienes which show high reactivity towards unsaturated molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Haihan Yan, Botao Wu, Junnian Wei, Wen-Xiong Zhang
Summary: In this study, rare-earth bis-(diazabutadiene) diradical complexes [(DAD)(2)RE-(BH4)] [RE = Yb (1), Sm (2)] were synthesized and studied. The different coordination geometries and exchange coupling of Yb(1) and Sm(2) resulted in different spectral behaviors, with the LLCT transition being clearly observed in Yb(1) but not in Sm(2). These findings expand the experimental examples of rare-earth bridged-diradical models in rare-earth systems.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Miaomiao Zhu, Zhengqi Chai, Ze-Jie Lv, Tianyu Li, Wei Liu, Junnian Wei, Wen-Xiong Zhang
Summary: In this study, we demonstrate the controllable cleavage of active and inert C-C bonds within biphenylene through the reaction with potassium graphite and rare-earth complexes with different metal centers. The Caryl-Caryl single bond is activated, producing 9-scandafluorene, when scandium is used as the reaction center. On the other hand, the aromatic ring in biphenylene undergoes ring contraction to form benzopentalene dianionic lutetium when Lu is the reaction center. The selectivity and reaction mechanism are elucidated by isolating intermediates and conducting DFT calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xuefeng Cong, Lin Huang, Zhaomin Hou
Summary: This Perspective focuses on recent advances in C-H functionalization with alkenes, allenes, and alkynes by half-sandwich rare-earth catalysts, including asymmetric transformations. The reaction generally proceeds through formal C-H addition to unsaturated C-C bonds, thus constituting a 100% atom-efficient route for the construction of new C-C bonds. Future outlooks in related areas are also described.
Article
Chemistry, Multidisciplinary
Yu Chen, Wei Liu, Xinlei Huangfu, Junnian Wei, Jiangxi Yu, Wen-Xiong Zhang
Summary: Organophosphorus compounds are widely used, but their traditional synthesis methods are complex and hazardous. It is significant to develop an environmentally-friendly and easy approach for constructing these compounds. In this study, a photoredox catalytic method was developed to produce phosphoryltriacetates using specific photocatalyst and blue light.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Xinlei Huangfu, Wei Liu, Hanhua Xu, Zhongzhen Wang, Junnian Wei, Wen-Xiong Zhang
Summary: The direct benzylation of P-4 promoted by visible light for the synthesis of tetrabenzylphosphonium bromides is presented here. Organophosphorus compounds (OPCs) have wide application in organic synthesis, material sciences, and drug discovery. The majority of phosphorus atoms in OPCs are derived from white phosphorus (P-4), and the large-scale preparation of OPCs usually involves multistep and environmentally toxic chlorine route. This study demonstrates the direct benzylation of P-4 using visible light, resulting in the synthesis of tetrabenzylphosphonium bromide from the readily available benzyl bromide. Additionally, the metallaphotoredox catalysis strategy is applied for the first time to functionalize P(4), expanding the application range of substituted benzyl bromide.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Aniket Mishra, Xuefeng Cong, Masayoshi Nishiura, Zhaomin Hou
Summary: Multisubstituted chiral 1-aminoindanes are important components in pharmaceuticals and bioactive molecules. The synthesis of chiral 1-aminoindanes is of great interest and importance, and the asymmetric[3 + 2] annulation of aldimines with alkenes through C-H activation is a promising method. This study reports the enantioselective [3 + 2] annulation of aromatic aldimines and alkenes via ortho-C(sp(2))-H activation using chiral half-sandwich scandium catalysts, which provides a straightforward route for the synthesis of multisubstituted chiral 1-aminoindanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yat-Ming So, Ching Tat To, Murali Mohan Guru, Takanori Shima, Zhaomin Hou
Summary: Carbon-carbon bond formation via coupling of two organic components is an important chemical transformation. In this study, a hydrodeoxygenative coupling of aromatic aldehydes was achieved to form bibenzyls by a titanium imide/hydride complex. The complex also demonstrated the ability to activate and functionalize N-2, as well as providing a platform for C-C bond formation using carbonyl compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Zhengqi Chai, Junnian Wei, Wen-Xiong Zhang
Summary: Rare-earth metallacycloheptatrienes, as key intermediates in metal-catalyzed [2 + 2 + 2] cycloaddition reactions, have been elusive until now. In this study, well-defined rare-earth metallacycloheptatrienes 2-Sc and 2-Lu were successfully obtained and characterized. The reactions and structures of these compounds were investigated.
Editorial Material
Chemistry, Multidisciplinary
Wei Liu, Wen-Xiong Zhang
Summary: In this study, a novel Zn(II) complex with visible-light absorption capabilities was reported, using a new method to construct such complexes that can respond to visible light.
Article
Chemistry, Multidisciplinary
Wei Liu, Yaqi Zhao, Wangyang Ma, Zhengqi Chai, Yibo Liang, Ze-Jie Lv, Ling Xu, Junnian Wei, Wen-Xiong Zhang
Summary: This article reports a reductive-elimination-type reaction at a rare-earth center, which represents a new elementary reaction in rare-earth organometallic chemistry and is expected to inspire the general development of rare-earth-promoted cross-nucleophilic coupling.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Miaomiao Zhu, Zhengqi Chai, Tianyu Li, Junnian Wei, Ze-Jie Lv, Wen-Xiong Zhang
Summary: We report the selective C-C coupling of two nitriles by rare-earth metal reduced naphthalene complexes to assemble rare-earth diazametallacyclopentadienes. Mechanistic studies reveal a different insertion-release-insertion sequence compared to the known oxidative cyclometallation process for transition metals, providing an alternative mechanism for metal-mediated reductive coupling of two nitriles. Furthermore, reactivity investigation shows that diazascandacyclopentadiene exhibits distinct reactions toward various compounds, indicating unique chemistry.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Jin-Qin Zhao, Liang-Liang Mao, Guo-Hui Zhang, Shun-Ze Zhan, Hongyan Xiao, Shaoguang Zhang, Chen-Ho Tung, Li-Zhu Wu, Huan Cong
Summary: A fluorescent polycatenated hydrogen-bonded organic framework (MEP-HOF) was developed using a C-3-symmetric rigid macrocycle as the exclusive building block. The tri-carboxylated macrocycles form supramolecular embraced pairs stabilized by intermolecular non-covalent interactions, further assembling into an interwoven three-dimensional H-bond network with a degree of catenation of seven. The MEP-HOF can be easily prepared and regenerated, and its fluorescent properties make it a sensitive sensor for nitrobenzene detection in water, with a detection limit of 61.8 +/- 2.2 ppb.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
