Article
Chemistry, Inorganic & Nuclear
Shintaro Takahashi, Raphal Nougue, Thibault Troadec, Antoine Baceiredo, Nathalie Saffon-Merceron, Vicenc Branchadell, Tsuyoshi Kato
Summary: A base-stabilized C-phosphonio-Si-amino-silyne 3 was synthesized through a coupling reaction between a silyliumylidene ion 1 and a P,S-bis-ylide 2. This new cationic silyne 3 shows high stability at room temperature (t1/2 = 7 days in THF) and unique reactivity due to the phosphonio substituent.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Elfie S. Cavalli, Thomas Mies, Henry S. Rzepa, Andrew J. P. White, Philip J. Parsons, Anthony G. M. Barrett
Summary: An efficient two-step procedure for synthesizing pyrimidine nucleosides is described. Firstly, a series of glycosyl 5-(aminomethylene)-1,3-dioxane-4,6-dione derivatives were prepared, followed by transacylation reaction to obtain uridine-5-carboxylic acid derivatives and related nucleosides.
Article
Chemistry, Multidisciplinary
Meng Li, Ruixue Zhang, Qiushan Gao, Huanfeng Jiang, Ming Lei, Wanqing Wu
Summary: Herein, a direct and efficient synthesis of diverse polysubstituted fused tetracyclic heterocycles with good functional group tolerance from diarylalkynes under different palladium catalytic systems is presented. The unprecedented intermolecular nucleopalladation of diarylalkynes through the highly selective sequential double insertion of isocyanide was achieved for the first time in this study. The practicality of this method was further demonstrated by the construction of various bioactive molecules and important structural motifs, with potential applications in materials science and biochemistry. In addition, density functional theory calculations revealed an interesting Pd walk during the cyclization process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Takuya Shimbayashi, Taiyou Ishige, Ken-ichi Fujita
Summary: A novel synthetic method for polysubstituted pyrroles from isocyanides and alpha,beta-unsaturated ketones using a rhodium catalyst and bis(pinacolato)diboron (B2pin2) is described. The selectivity for different pyrrole products can be controlled by adjusting the reaction temperature and isocyanide concentration. The 2-imidoylpyrroles obtained can be hydrolyzed to isolate 2-formylpyrroles, which are naturally abundant and useful in synthesis. Deuterium-labelling experiments suggest that rhodium hydride intermediates are involved in the catalytic cycle.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Michael Fragkiadakis, Paraskevi-Kleio Anastasiou, Marios Zingiridis, Marios E. Triantafyllou-Rundell, Atilio Reyes Romero, Constantinos C. Stoumpos, Constantinos G. Neochoritis
Summary: Chemists are intrigued by macrocycles due to their structure and applications, but there is a lack of efficient and sustainable synthetic methods for straightforward access to them. This study introduces a rapid macrocyclization method using a two-step, one-pot approach based on orthogonal multicomponent reaction (MCR) tactics. By utilizing Ugi and Groebke-Blackburn-Bienayme reactions with isocyanides tethered to alkyl tosylates, medium sized macrocycles that are difficult to achieve can be obtained. Single crystal structures reveal conformational reorganization through intramolecular hydrogen bonding, and modeling studies profile the synthesized libraries.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ming-Yao Huang, Shou-Fei Zhu
Summary: In comparison to common carbene insertion reactions, the overlooked uncommon carbene insertion reactions have been gaining more attention recently for their synthetic potential. The perspective reviews the history and latest advances of uncommon carbene insertion reactions, discusses their potential applications and challenges, and provides an outlook for this promising field.
Review
Chemistry, Applied
Zahra Tashrifi, Mohammad Mohammadi Khanaposhtani, Fatemeh Gholami, Bagher Larijani, Mohammad Mahdavi
Summary: Isocyanides have been widely used in organic synthesis to prepare N-heterocycles based on their carbene-like reactivity. While single isocyanide reactions are popular, reactions involving two or more isocyanides are relatively rare. In this review, we categorize and classify the literature on reactions involving two or more isocyanides, especially double isocyanide insertions, under metal-catalyzed or metal-free conditions from 2014 to 2022.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Miao Tian, Jianying Zhang, Lulu Guo, Chunming Cui
Summary: This study describes the isolation of a novel 1,2-dilithiodisilene and its potential as a synthetic reagent for novel silicon multiply bonded species. The results highlight the significant electronic effects of boryl substituents on silicon multiple bonding structures.
Review
Chemistry, Applied
Zhen Zhang, Pengpeng Tan, Wenxu Chang, Zhenhua Zhang
Summary: Transition-metal-catalyzed cross-coupling reaction of azides with isocyanides has become an efficient method for preparing carbodiimides, and it has broad applications in constructing nitrogen-containing structures, making it a popular sequential reaction method. The recent advances in catalytic cascade reactions involving a coupling process are highlighted in this review.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Polymer Science
Paul van den Tempel, Emiel O. van der Boon, Jozef G. M. Winkelman, Antonina V. Krasnikova, Daniele Parisi, Peter J. Deuss, Francesco Picchioni, Ranjita K. Bose
Summary: The furan-maleimide Diels-Alder chemistry is a useful tool for designing thermo-reversible click networks. In this study, a new reaction in furan-maleimide click networks, called the Double-Diels-Alder reaction (DDA), was reported. This reaction forms extra linkages between Diels-Alder adducts and non-reacted furan groups, resulting in stronger materials but reducing thermal recycling efficiency. The study revealed that the DDA reaction can occur in both intramolecular and intermolecular fashion, and it exhibits reversibility like the regular Diels-Alder reaction. The importance of the DDA reaction in furan-maleimide click networks may be easily overlooked, leading to unexpected reactivity in these systems.
Review
Chemistry, Organic
Yeming Wang, Chaoqun Zhang, Shizhe Li, Lihui Liu, Xiaodong Feng, Gang Liu
Summary: In recent years, the efficiency and selectivity of silver-catalyzed and silver-promoted isocyanide reactions have drawn much attention due to their ability to form diverse new bonds. This review highlights the recent progress in the synthesis of five-membered heterocyclic compounds, six-membered heterocyclic compounds, fused cyclic compounds, and linear nitrogen-containing compounds.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Astronomy & Astrophysics
Joshua T. Carder, Alec Paulive, Eric Herbst
Summary: The formation of complex organic molecules (COMs) in interstellar conditions is influenced by various processes in both the gas and solid phases. This study focuses on the influence of electronically excited metastable species on COM formation through insertion-type reactions. These reactions involve the insertion of a chemical entity into an existing chemical bond, allowing for rapid reactions even under cold, dark cloud conditions. The relative importance of this newly added process is evaluated by comparing it with existing suggested pathways.
MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Li Li, Chenggang Mi, Guanwang Huang, Meirong Huang, Yuyi Zhu, Shao-Fei Ni, Zhaofeng Wang, Yong Huang
Summary: In this study, a new approach based on an I(III)/S(VI) reagent is described, which enables the cascade insertion of heteroatoms by sequentially generating two α-heteroatom-substituted metal carbenes in one reaction. This method allows for the synthesis of a wide range of α,α-O,O-, α,α-O,N-, and α,α-N,N-substituted ketones under mild conditions, and demonstrates the ability to simultaneously introduce multiple functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Bing-Bing Sun, Kun Liu, Quan Gao, Wei Fang, Shuang Lu, Chun-Ru Wang, Chuan-Zhi Yao, Hai-Qun Cao, Jie Yu
Summary: This article reports on a strategy that enables enantioselective Ugi four-component and Ugi-azide reactions using anionic stereogenic-at-cobalt(III) complexes as catalysts. By controlling the generation and trapping of key nitrilium intermediates, highly enantioselective alpha-acylamino amides and alpha-aminotetrazoles can be obtained.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Cyrille Costentin
Summary: Molecular catalysis of electrochemical reactions is becoming increasingly important in modern energy challenges involving the activation of small molecules. Clarification of the notion of overpotential is crucial for designing the best catalyst for targeted reactions.
Article
Chemistry, Multidisciplinary
Paresh Kumar Majhi, Volker Huch, David Scheschkewitz
Summary: The synthesis and isolation of a stable potassium silagermenide compound with a Si=Ge bond as a suitable synthon for functional silagermenes has been reported. X-ray crystallographic analysis, UV/Vis spectroscopy, and DFT calculations confirmed a significant degree of pi-conjugation between N=C and Si=Ge double bonds in the compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Lukas Klemmer, Anna-Lena Thoemmes, Michael Zimmer, Volker Huch, Bernd Morgenstern, David Scheschkewitz
Summary: The study reports thermally induced, transition-metal-free metathesis of unsymmetrically substituted digermenes. The use of tethered auxiliary donors helps stabilize the transient germylene fragments, promoting the metathesis reaction. Density functional theory calculations reveal the thermodynamic driving force of the metathesis and the crucial role of tethered donors in the reaction. The bridged tetragermadiene precursor can also undergo heavier acyclic diene metathesis polymerization, similar to the carbon case, resulting in polydigermene formation.
Review
Chemistry, Multidisciplinary
Yannic Heider, David Scheschkewitz
Summary: This review provides a comprehensive overview of the state of the art in the synthesis of molecular silicon clusters, which are divided into three different categories. It emphasizes the importance of functionalization as a necessary prerequisite for the design and construction of more extended systems.
Article
Chemistry, Multidisciplinary
Paresh Kumar Majhi, Michael Zimmer, Bernd Morgenstern, Volker Huch, David Scheschkewitz
Summary: Transition metal p-allyl complexes play important roles in various catalytic and stoichiometric allylation reactions. In this study, the first transition metal complex of a heavier allylic pi-system was reported, providing insights into the formation process and coordination behavior of the complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Paresh Kumar Majhi, Michael Zimmer, Bernd Morgenstern, David Scheschkewitz
Summary: A novel sesquimetallic complex containing a Si2Ge cyclopropene has been synthesized, showing a unique coordination mode where the sigma-component of the Ge = Si double bond acts as both a donor and acceptor, allowing for the formation of a nearly unsupported Si-Ge pi-bond. This complex can be easily modified and substituted with different functional groups, providing access to a variety of nickel complexes with high yields.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Andreas T. Kell, Naim M. Obeid, Prasenjit Bag, Michael Zimmer, Volker Huch, David Scheschkewitz
Summary: The regiodivergent reaction of phenylacetylene with various disilenes and bridged tetrasiladienes was studied, revealing that the regioselectivity of the [2+2] cycloaddition strongly depends on the nature of the substituent R. The presence of catalytic quantities of base suppresses cycloaddition in favor of the formal CH addition of phenylacetylene. Intermediacy of an alkynyl-substituted disilanyl lithium suggests a carbolithiation pathway for the net CH addition.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2021)
Article
Chemistry, Inorganic & Nuclear
Thomas Buettner, Konstantin Weisshaar, Philipp Willmes, Volker Huch, Bernd Morgenstern, Rolf Hempelmann, David Scheschkewitz
Summary: The synthesis of p-methylthio-functionalized disilenes with (oligo)phenylene-linkers of different sizes was reported, with Si-29 NMR and UV/vis data suggesting that the linker-size only moderately affects the Si=Si moiety. Cyclic voltammetry showed an increasing number of reduction events with the number of phenylene rings, clearly associated with the oligo(phenylene) linking unit. Significant differences in the exchange current density of oxidation and reduction reactions were observed between the prepared disilenes using linear sweep voltammetry with a rotating disc electrode.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2021)
Article
Chemistry, Inorganic & Nuclear
Marcel Lambert, Nadine E. Poitiers, Volker Huch, Andrea Goforth, David Scheschkewitz
Summary: The first silicon-carbon hybrid ladderanes with highly distorted ring systems and long silicon-carbon bridgehead bonds were obtained.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Multidisciplinary
Nadine E. Poitiers, Volker Huch, Bernd Morgenstern, Michael Zimmer, David Scheschkewitz
Summary: This study reports the growth of stable siliconoid clusters through a series of substitution, rearrangement, and reduction reactions with a single germanium atom. The findings are significant for understanding nucleation processes in gaseous and condensed phases.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Hanna Huebner, Bart-Jan Niebuur, Thomas Buettner, Marcus Koch, Bernd Stuehn, Tobias Kraus, David Scheschkewitz, Markus Gallei
Summary: This study characterizes the self-assembled structures of PDMSB-b-P2VP block copolymer in different solvents and evaluates its response to different solvents and temperatures. The influence of additional solvents, temperature, and ultrasonication on colloidal dispersion is investigated. Additionally, the introduction of surfactants in the solvent evaporation method leads to a plethora of additional colloidal structures.
Article
Chemistry, Inorganic & Nuclear
Marc Hunsicker, Nadine E. Poitiers, Volker Huch, Bernd Morgenstern, Michael Zimmer, David Scheschkewitz
Summary: A new potential model system for silicon monoxide has been synthesized by connecting an unsaturated silicon cluster with a polyhedral silsequioxane cage. The stoichiometry between silicon and oxygen in this model system is 14:12.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Multidisciplinary
Philipp Dabringhaus, Silja Zedlitz, Luisa Giarrana, David Scheschkewitz, Ingo Krossing
Summary: Schnockel's [(AlCp*)(4)] and Jutzi's [SiCp*][B(C6F5)(4)] are important in modern main-group chemistry with various applications in synthesis and catalysis. However, the reactivity between AlCp* and [SiCp*](+) has not been explored. In this study, their reaction was investigated and complex salts [Cp*Si(AlCp*)(3)][WCA] were obtained. The tetrahedral [SiAl3](+) core not only represents a rare example of a low-valent silicon-doped aluminium-cluster, but also provides a convenient preparative entry towards low-valent Si-Al clusters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Taiki Imagawa, Luisa Giarrana, Diego M. Andrada, Bernd Morgenstern, Masaaki Nakamoto, David Scheschkewitz
Summary: By a series of addition and reduction reactions, the synthesis of a structurally rare silapyramidane compound was achieved from an amidinate-supported silylene and tetrakis(trimethylsilyl)cyclobutadiene as starting materials. The silapyramidane compound exhibited an unusually shielded 29Si NMR resonance at -448.3 ppm for the apex silicon atom. Treatment of the silapyramidane with Fe2(CO)9 resulted in the formation of the corresponding silapyramidane-iron complex. Moreover, the silapyramidane also underwent a reaction with the cyclobutadiene starting material to afford a fluorescent spirobis(silole) compound.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Philipp Grewelinger, Tim Wiesmeier, Carsten Praesang, Bernd Morgenstern, David Scheschkewitz
Summary: A straightforward synthesis of the first peraryl diboriranide was reported, demonstrating its preference for s-type coordination modes towards main group and transition metal centers. The synthesis involved the preparation of the non-classical diborirane from a readily available 1,2-dichlorodiborane(4) and subsequent conversion to the peraryl diboriranide lithium salt in three steps. Representative complexes with tin, copper, gold, and zinc were prepared and characterized to illustrate the reactivity and complexation behavior of the diboriranide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Thomas Buettner, Oliver Janka, Volker Huch, Debabrata Dhara, Anukul Jana, David Scheschkewitz
Summary: In this study, a new single source chemical vapor deposition (CVD) method was developed for the synthesis of binary iron-germanium thin films. The technique allows for the preparation of uniform and dense Fe(x)G(e)y films under standard CVD conditions, without the need for harsh conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)