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Synthesis and reactivity of N-heterocyclic carbene (NHC)-supported heavier nitrile ylides† † Electronic supplementary information (ESI) available. CCDC 2300364–2300367. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc06430a

ABSTRACT:

SUBMITTER: Sarkar D

PROVIDER: S-EPMC10866356 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

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1-Azahomocubane† † Electronic supplementary information (ESI) available. CCDC 2177501. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc00001j

Project description:Highly strained cage hydrocarbons have long stood as fundamental molecules to explore the limits of chemical stability and reactivity, probe physical properties, and more recently as bioactive molecules and in materials discovery. Interestingly, the nitrogenous congeners have attracted much less attention. Previously absent from the literature, azahomocubanes, offer an opportunity to investigate the effects of a nitrogen atom when incorporated into a highly constrained polycyclic environment. Herein disclosed is the synthesis of 1-azahomocubane, accompanied by comprehensive structural characterization, physical property analysis and chemical reactivity. These data support the conclusion that nitrogen is remarkably well tolerated in a highly strained environment. 1-Azahomocubane has been prepared 56 years after the parent hydrocarbon. Introduction of a nitrogen atom into this constrained polycyclic environment resulted in minimal changes to the framework geometry, with s-character of the nitrogen lone pair increasing due to strain.

| S-EPMC10016339 | biostudies-literature

Catalytic electron drives host–guest recognition† † Electronic supplementary information (ESI) available. CCDC 2096046. For ESI and crystallographic data in CIF or other electronic format see https://doi.org/10.1039/d2sc01342h

Project description:Electron injection is demonstrated to trigger electrocatalytic chain reactions capable of releasing a solvent molecule and forming a redox active guest molecule. One-electron reduction of a hydroxy anthrone derivative (AQH–CH2CN) results in the formation of an anthraquinone radical anion (AQ˙−) and acetonitrile (CH3CN). The resulting fragment of AQ˙− exhibits high stability under mild reducing conditions, and it has enough reducing power to reduce the reactant of AQH–CH2CN. Hence, subsequent electron transfer from AQ˙− to AQH–CH2CN yields the secondary AQ˙− and CH3CN, while the initial AQ˙− is subsequently oxidized to AQ. Overall, the reactants of AQH–CH2CN are completely converted into AQ and CH3CN in sustainable electrocatalytic chain reactions. These electrocatalytic chain reactions are mild and sustainable, successfully achieving catalytic electron-triggered charge-transfer (CT) complex formation. Reactant AQH–CH2CN is non-planar, making it unsuitable for CT interaction with an electron donor host compound (UHAnt2) bearing parallel anthracene tweezers. However, conversion of AQH–CH2CN to planar electron acceptor AQ by the electrocatalytic chain reactions turns on CT interaction, generating a host CT complex with UHAnt2 (AQ ⊂ UHAnt2). Therefore, sustainable electrocatalytic chain reactions can control CT interactions using only a catalytic amount of electrons, ultimately affording a one-electron switch associated with catalytic electron-triggered turn-on molecular recognition. The reactants of AQH–CH2CN are converted into AQ and CH3CN in sustainable electrocatalytic chain reactions, successfully achieving catalytic electron-triggered charge-transfer (CT) complex formation.

| S-EPMC9093170 | biostudies-literature

Terminal dysprosium and holmium organoimides† † Electronic supplementary information (ESI) available. CCDC 2312212–2312226. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc06584g

Project description: Not available

| S-EPMC10915843 | biostudies-literature

An unprecedented azobenzene-based organic single-component ferroelectric† † Electronic supplementary information (ESI) available. CCDC 2144165 and 2144166. For ESI and crystallographic data in CIF or other electronic format see https://doi.org/10.1039/d2sc00689h

Project description:Organic single-component ferroelectrics, as an important class of metal-free ferroelectrics, are highly desirable because of their easy processing, mechanical flexibility, and biocompatibility. However, although nearly 50 years have passed since the discovery of photochromism in azobenzene-doped cholesteric liquid crystals, ferroelectricity has never been found in azobenzene-based crystals. Here, we use an amino group to substitute a fluorine atom of 2,2′,4,4′,6,6′-hexafluoroazobenzene, which successfully introduces ferroelectricity into 2-amino-2′,4,4′,6,6′-pentafluoroazobenzene (APFA). APFA shows an extremely high Curie temperature (Tc) of 443 K, which is outstanding among single-component ferroelectrics. It also exhibits an indirect optical band gap of 2.27 eV as well as photoisomerization behavior between the trans-form and the cis-form triggered by pedal motion. To our knowledge, APFA is the first azobenzene-based ferroelectric crystal. This work opens an avenue to design excellent single-component ferroelectrics and will inspire the exploration of azobenzene-based ferroelectrics for promising applications in biofriendly ferroelectric devices. The first azobenzene-based organic single-component ferroelectric 2-amino-2′,4,4′,6,6′-pentafluoroazobenzene was designed, which shows an exceptionally high Curie temperature (Tc) of 443 K.

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Enantioselective nickel-catalyzed Mizoroki–Heck cyclizations of amide electrophiles† † Electronic supplementary information (ESI) available. CCDC 2271421. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc05797f

Project description: Not available

| S-EPMC10866352 | biostudies-literature

Ambiphilicity of ring-expanded N-heterocyclic carbenes† † Electronic supplementary information (ESI) available. CCDC 2291449, 2291450–2291455. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc04543a

Project description: Not available

| S-EPMC10915854 | biostudies-literature

On pyridine chloronium cations† † Electronic supplementary information (ESI) available. CCDC 2223424, 2223431, 2223423, 2223425, 2223439 and 2223421. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d2sc06757a

Project description:We present the first solid-state structural evidence of mono- and bis(pyridine)chloronium cations. The latter was synthesized from a mixture of pyridine, elemental chlorine and sodium tetrafluoroborate in propionitrile at low temperatures. The mono(pyridine) chloronium cation was realized with the less reactive pentafluoropyridine, using ClF, AsF5, and C5F5N in anhydrous HF. During the course of this study, we also investigated pyridine dichlorine adducts and found a surprising disproportionation reaction of chlorine that depended on the substitutional pattern of the pyridine. Electron richer dimethylpyridine (lutidine) derivatives favor full disproportionation into a positively and a negatively charged chlorine atom which forms a trichloride monoanion, while unsubstituted pyridine forms a 1 : 1 py·Cl2 adduct. The lutidine elephants are pulling apart a dichlorine molecule and stabilizing the corresponding chloronium cation. The remaining chloride forms a trichloride anion. Unsubstituted pyridine, however, only forms a strongly polarized dichlorine adduct.

| S-EPMC9977394 | biostudies-literature

Computation meets experiment: identification of highly efficient fibrillating peptides† † Electronic supplementary information (ESI) available: CCDC 2174444–2174447. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3ce00495c

Project description:Self-assembling peptides are of huge interest for biological, medical and nanotechnological applications. The enormous chemical variety that is available from the 20 amino acids offers potentially unlimited peptide sequences, but it is currently an issue to predict their supramolecular behavior in a reliable and cheap way. Herein we report a computational method to screen and forecast the aqueous self-assembly propensity of amyloidogenic pentapeptides. This method was found also as an interesting tool to predict peptide crystallinity, which may be of interest for the development of peptide based drugs. 8000 pentapeptides were computed though CG-MD starting from the model sequence DFNKF. Based on experimental validation, theoretical conditions (solubility and aggregation propensity) which may favor crystallization or fibrillation were identified.

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Asymmetric dearomative cyclopropanation of naphthalenes to construct polycyclic compounds† † Electronic supplementary information (ESI) available. CCDC 2191640 and 2191583. For ESI and crystallographic data in CIF or other electronic format see: https://doi.org/10.1039/d2sc04509e

Project description:Catalytic asymmetric dearomatization (CADA) reactions is an important synthetic method for constructing enantioenriched complex cyclic systems from simple aromatic feedstocks. However, the CADA reactions of nonactivated arenes, such as naphthalenes and benzenes, have been far less explored than those of electronically activated arenes, such as phenols, naphthols and indoles. Herein, we disclose an asymmetric dearomative cyclopropanation of naphthalenes for the rapid construction of polycyclic compounds. With chiral dirhodium carboxylate as a catalyst, the dearomative cyclopropanation proceeded smoothly under mild conditions and afforded benzonorcaradiene-containing tetracycles in good yield and high enantioselectivity (up to 99% ee). Three stereogenic centers, including two all-carbon quaternary centers, were created in the dearomatization reaction. Moreover, a variety of functional groups are well-tolerated in the reaction. The products could be readily converted into other complex polycycles while maintaining the high ee value. An enantioselective dearomative cyclopropanation of naphthalenes has been developed, which constructed a range of tetracyclic compounds bearing multichiral centers in high enantioselectivity.

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A metal-free strategy to construct fluoroalkyl–olefin linkages using fluoroalkanes† † Electronic supplementary information (ESI) available. CCDC 2299679. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc05616c

Project description: Not available

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