Among the perfluorinated substituents of organic compounds, the pentafluorosulfanyl (SF5) group received remarkable attention in the past few decades due to its particular properties such as high ...thermal, chemical and metabolic stability, high density, high group electronegativity, high lipophilicity, and interesting effects on the biological activity of relevant compounds. This review retraces the massive progress made towards the preparation and application of reagents like SF5X (X = F, Cl, Br) for the synthesis of SF5-containing small building blocks designed for the construction of complex aliphatic molecules potentially applicable in drug and pesticide design as well as in materials sciences.
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Recently, acceptor–donor–acceptor (A–D–A) small molecules have emerged as promising nonfullerene acceptors (NFAs) for organic solar cells and have attracted great attention. The carbon‐bridged ...(C‐bridged) ladder‐type D unit plays a crucial role in developing high‐performance A–D–A NFAs. However, the medium electron‐donating capability of C‐bridged units is unfavorable for making NFAs with strong light‐harvesting capability. In this regard, carbon–oxygen‐bridged (CO‐bridged) ladder‐type units present advantages in developing strong light‐absorbing NFAs. Here, recent progress in the newly emerging CO‐bridged NFAs is highlighted. The synthetic methods for the polycyclic CO‐bridged building blocks are introduced. The photovoltaic performance for CO‐bridged NFAs is summarized and discussed. Perspectives on developing high‐performance CO‐bridged‐NFA‐based solar cells are made.
Thanks to the strong electron‐donating capability of carbon–oxygen‐bridged (CO‐bridged) ladder‐type building blocks, CO‐bridged nonfullerene acceptors (NFAs) present low bandgaps and strong light‐harvesting capability, delivering high short‐circuit current density (>28 mA cm−2) and high power conversion efficiency (>14% for single‐junction and >17% for tandem) in organic solar cells.
In the field of medicinal chemistry, the precise installation of a trideuteromethyl group is gaining ever‐increasing attention. Site‐selective incorporation of the deuterated “magic methyl” group can ...provide profound pharmacological benefits and can be considered an important tool for drug optimization and development. This review provides a structured overview, according to trideuteromethylation reagent, of currently established methods for site‐selective trideuteromethylation of carbon atoms. In addition to CD3, the selective introduction of CD2H and CDH2 groups is also considered. For all methods, the corresponding mechanism and scope are discussed whenever reported. As such, this review can be a starting point for synthetic chemists to further advance trideuteromethylation methodologies. At the same time, this review aims to be a guide for medicinal chemists, offering them the available C−CD3 formation strategies for the preparation of new or modified drugs.
“3 D” drug development: The deuterated “magic methyl” group is attracting increased interest in pharmaceutical industry. In this review, we discuss the currently available methods for C−CD3 bond forming reactions and classify them according to the trideuteromethylation reagent. The mechanisms, scope and limitations of each method are considered in order to provide a guide for targeted trideutermethylation.
Formyl MIDA boronate has been known to be an elusive type of acylboronate that has not been obtained to date. In this work, an approach to the one‐pot preparation and chemical transformations of ...formyl MIDA boronate were developed to provide new types of α‐functionalized organoboron compounds. Among them are acylboronate reagents which present boron‐substituted analogues of ynones and β‐dicarbonyl compounds. The developed synthetic procedures, utilizing formyl MIDA boronate, are tolerant to diverse functional groups, making this reagent an advantageous C1 building block for extending the scope of organoboron chemistry.
One‐pot preparation and chemical reactions of formyl MIDA boronate are described in this work. New types of α‐functionalized organoboron compounds, including boron‐substituted analogues of ynones and β‐dicarbonyl compounds, are synthesized. The method demonstrates high tolerance to diverse functional moieties, making formyl MIDA boronate a valuable C1 building block for extending the scope of organoboron chemistry.
Base Metal Catalyzed Isocyanide Insertions Collet, Jurriën W.; Roose, Thomas R.; Ruijter, Eelco ...
Angewandte Chemie International Edition,
January 7, 2020, Volume:
59, Issue:
2
Journal Article
Peer reviewed
Open access
Isocyanides are diverse C1 building blocks considering their potential to react with nucleophiles, electrophiles, and radicals. Therefore, perhaps not surprisingly, isocyanides are highly valuable as ...inputs for multicomponent reactions (MCRs) and other one‐pot cascade processes. In the field of organometallic chemistry, isocyanides typically serve as ligands for transition metals. The coordination of isocyanides to metal centers alters the electronic distribution of the isocyano moiety, and reaction pathways can therefore be accessed that are not possible in the absence of the metal. The tunable reactivity of the isocyanide functional group by transition metals has evolved into numerous useful applications. Especially palladium‐catalyzed isocyanide insertion processes have emerged as powerful reactions in the past decade. However, reports on the use of earth‐abundant and cheap base metals in these types of transformations are scarce and have received far less attention. In this Minireview, we focus on these emerging base metal catalyzed reactions and highlight their potential in synthetic organic chemistry. Although mechanistic studies are still scarce, we discuss distinct proposed catalytic cycles and categorize the literature according to 1) the (hetero)atom bound to and 2) the type of bonding with the transition metal in which the (formal) insertion occurs.
Back to basics: Base metal catalyzed processes involving isocyanide insertion have recently evolved as promising cross‐coupling reactions. While mechanistic studies are still scarce, proposed catalytic cycles are discussed in this Minireview and the literature is categorized accordingly. This should facilitate the development of new processes to efficiently assemble high added‐value compounds.
The Front Cover shows the main building of the Vernadsky National Library of Ukraine located in Kyїv, as well as two constellations depicting novel cis‐ and trans‐1,3‐disubstituted cyclobutane ...building blocks bearing CF3, CHF2, or CH2F groups. The photo was taken by Bohdan Vashchenko in late 2022 when the synthetic part of this work had been finalized. Despite the building being located deep in the city, the night stars were clearly visible even in the unedited version of the picture due to the special circumstances of that period. The invaluable help of Vladyslava Prykhodko with artwork preparation is appreciated. More information can be found in the Research Article by O. O. Grygorenko et al.
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•Successful trifluoromethylation with readily available Iron(II) triflate as a robust photocatalyst.•Bench-stable CF3SO2Na as a CF3 source under blue light irradiation.•Potential ...functional group tolerance and applicable for gram-scale reactions.•Trifluoromethylation of rivaroxaban intermediate and a few bioactive compounds.•Preparation of Teriflunomide drug.
The trifluoromethyl group (-CF3) containing motifs are valuable leads for the small molecule drug discovery process and have multiple applications in medicine, agriculture, and material science. Not many CF3-containing motifs are commercially accessible; therefore, it is critical to design more advanced building blocks. In this work, we demonstrate an oxidant-free, scalable, and user-friendly protocol for the direct C(sp2)-H trifluoromethylation of functionalized arenes using Iron(II) triflate as a robust photocatalyst and bench-stable CF3SO2Na (1.5 equiv.) as a CF3 source under blue light irradiation. This method was extrapolated to >30 examples and compatible with potential functional groups (-NO2, -NH2, OH, -CHO, -CO2H, halogens, etc.). Notably, the utility of this approach is showcased for the synthesis of novel CF3-containing synthetic building blocks and a few bioactive compounds.
Focusing on strategic agility and business model concepts, the present paper proposes a framework for recognising common strategies, activities and paths to business model reconfiguration developed ...through the activation of a set of micro-capabilities. We argue that successful companies nurture specific capabilities in order to act proactively and to reach strategic agility and direct these to specific key elements of the business model (building blocks), thus enabling the renewing of the entire business model.
The methodology is a multiple case study analysis of four successful companies in different industries. We identified three main classes of capabilities for strategic agility and we explored which ones are valid and how they can be activated in a company's business model through an in-depth within-case and cross-case analysis.
Results show that strategy innovation capabilities could be focused on motto and value offer, research and development and social responsibility building blocks; resource capitalisation capabilities on education and knowledge, management and human resource building blocks, and networking capabilities on branding and retail and network building blocks.
From a literature point of view, we contributed to the ongoing debate about business model change and critical capabilities, by investigating the “black box” of business models. From the practical point of view, the linkage between capabilities and the building blocks of the business model is important in order to capitalise on resources and time, focusing on specific actions and specific areas of the business model.
•Three macro-capabilities for business model reconfiguration are identified.•Capabilities should focus on specific building blocks to achieve strategic agility.•A model showing the effects of focusing capabilities on building blocks is obtained.
Silicon nanoparticles (Si NPs) have been considered as promising anode materials for next‐generation lithium‐ion batteries, but the practical issues such as mechanical structure instability and low ...volumetric energy density limit their development. At present, the functional energy‐storing architectures based on Si NPs building blocks have been proposed to solve the adverse effects of nanostructures, but designing ideal functional architectures with excellent electrochemical performance is still a significant challenge. This study shows that the effective stress evolution management is applied for self‐assembled functional architectures via cross‐scale simulation and the simulated stress evolution can be a guide to design a scalable self‐assembled hierarchical Si@TiO2@C (SA‐SiTC) based on core–shell Si@TiO2 nanoscale building blocks. It is found that the carbon filler and TiO2 layer can effectively reduce the risk of cracking during (de)lithiation, ensuring the stability of the mechanical structure of SA‐SiTC. The SA‐SiTC electrode shows long cycling stability (842.6 mAh g−1 after 1000 cycles at 2 A g−1), high volumetric capacity (174 mAh cm−3), high initial Coulombic efficiency (80.9%), and stable solid‐electrolyte interphase (SEI) layer. This work provides insight into the development of the structural stable Si‐based anodes with long cycle life and high volumetric energy density for practical energy applications.
Effective stress evolution management is applied for self‐assembled functional architectures via cross‐scale simulation and the simulated stress evolution can be a guide to design a scalable self‐assembled hierarchical Si@TiO2@C (SA‐SiTC) based on core–shell Si@TiO2 nanoscale building blocks. This work provides insight into the development of the structural stable Si‐based anodes with long cycle life and high volumetric energy density for practical energy applications
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