The Tetrafluoroethylene-Mediated Ring-Closing Metathesis: Enabling Unfavored Reactions.

While ring-closing metathesis (RCM) is a powerful method for constructing medium and large cyclic alkenes, its application to the synthesis of heterocycles faces considerable limitations. For instance, RCM of divinyloxyalkanes does not proceed under the conventional conditions of RCM. The challenge lies in the formation of stable Fischer-type carbene intermediates with heteroatom(s) bound to the carbene carbon, impeding subsequent metathesis.

Exceptionally Short Tetracoordinated Carbon-Halogen Bonds in Hexafluorodihalocubanes.

Molecules that contain bonds whose length significantly deviates from the average are of interest in the context of understanding the nature and limits of the chemical bonds. However, it is difficult to disentangle the individual contributions of the multiple factors that give rise to such bond-length deviations as reports on such molecules remain scarce. In the present study, we have succeeded in synthesizing hexafluorodihalocubanes of the type CFX () (X = Cl (), Br (), I ()), which represent a new series of molecules with unusual C(sp)-halogen bonds.

Photoinduced charge separation at heterojunctions between two-dimensional layered materials and small organic molecules.

p-n heterojunctions are fundamental components for electronics and optoelectronics, including diodes, transistors, sensors, and solar cells. Over the past few decades, organic-inorganic p-n heterojunctions have garnered significant interest due to the diverse properties they exhibit, which are a result of the limitless combinations of organic molecules and inorganic materials. This review article concentrates on photoinduced charge separation and photocurrent generation at heterojunctions between two-dimensional layered materials and structurally well-defined organic small molecules.

Molecular donor-acceptor linked systems as models for examining their interactions in excited states.

Molecular donor-acceptor (D-A) linked systems have attracted significant attention due to their potential to address D-A interactions in excited states. In these systems, it is crucial to understand the interplay between electrons and spin behaviors, atomic nucleus movements (including vibration, rotation, fluctuation, and transfer), and collective motion (electron-phonon coupling) over time. Through intentional manipulation of locally excited, charge-transfer excited, and charge-separated states, along with modulation of dynamic effects (enhancement or restraint), we expect to unlock the full potential of D-A systems for photofunctions in electronics, energy, healthcare, and functional materials.

Diverse Strategies for Modulating Insulin Resistance: Causal or Consequential Inference on Metabolic Parameters in Treatment-Naïve Subjects with Type 2 Diabetes.

: The objective of this study is to investigate how different therapies modulating insulin resistance, either causally or consequently, affect metabolic parameters in treatment-naïve subjects with T2DM. : A total of 212 subjects were assigned to receive either a tight Japanese diet ( = 65), pioglitazone at doses ranging from 15-30 mg/day ( = 70), or canagliflozin at doses ranging from 50-100 mg/day ( = 77) for a duration of three months. Correlations and changes (Δ) in metabolic parameters relative to insulin resistance were investigated.

Alogliptin: a DPP-4 inhibitor modulating adipose tissue insulin resistance and atherogenic lipid.

Aims: The purpose of this study is to investigate the regulation of adipose tissue insulin resistance with DPP-4 inhibitors in treatment-naive subjects with T2DM and to examine its relation to other diabetic parameters.

Subjects And Methods: A total of 147 subjects were treated with alogliptin 12.5-25 mg/day (n = 55), sitagliptin 25-50 mg/day (n = 49), or teneligliptin 10-20 mg/day (n = 43) monotherapy for 3 months.

Regulation of Adipose Tissue Insulin Resistance and Diabetic Parameters in Drug Naïve Subjects with Type 2 Diabetes Treated with Canagliflozin Monotherapy.

The objective of this study is to investigate the link between the baseline/changes of body weight and those of diabetic parameters during treatment with an SGLT-2 inhibitor. Drug naïve subjects with T2DM received canagliflozin monotherapy for 3 months. Adipo-IR was selected as the significant factor responsible for the changes of (Δ)BMI with this drug.

The Fluorocarbene Exploit: Enforcing Alternation in Ring-Opening Metathesis Polymerization.

Fluoroalkenes are known to be notoriously reluctant substrates for olefin metathesis due to the generation of thermodynamically stable Fischer-type fluorocarbene intermediates, which invariably fail to undergo further reaction. In the present disclosure, we find that fluorine substitution on the sp carbon also strictly suppresses homopolymerization of norbornene derivatives (NBEs), and this can be harnessed to achieve alternating ring-opening metathesis polymerization (ROMP) with an appropriately electron-rich comonomer. Dihydrofuran (DHF) is thereby shown to undergo alternating ROMP with fluorinated norbornenes, the perfectly alternating structure of the resulting copolymer having been unambiguously elucidated by H, F, and C NMR analyses.

Electron in a cube: Synthesis and characterization of perfluorocubane as an electron acceptor.

Fluorinated analogs of polyhedral hydrocarbons have been predicted to localize an electron within their cages upon reduction. Here, we report the synthesis and characterization of perfluorocubane, a stable polyhedral fluorocarbon. The key to the successful synthesis was the efficient introduction of multiple fluorine atoms to cubane by liquid-phase reaction with fluorine gas.

Synthesis of Crystalline CF -Rich Perfluoropolyethers from Hexafluoropropylene Oxide and (Trifluoromethyl)Trimethylsilane.

The synthesis of a CF -rich perfluoropolyether (PFPE) is achieved via the fluoride-catalyzed reaction of hexafluoropropylene oxide (HFPO) with (trifluoromethyl)trimethylsilane (TMSCF , so-called Ruppert-Prakash reagent). Nucleophilic addition of a CF anion to HFPO affords an acyl fluoride via the ring-opening of HFPO, followed by fluoride elimination. Further addition of CF anions to the acyl fluoride gives tertiary perfluoroalkoxide, which attacks HFPO to regenerate an acyl fluoride.

Highly Active Cross-Metathesis of Tetrafluoroethylene with a Seven-Membered N-Heterocyclic-Carbene-Ruthenium Catalyst.

A drastic increase in catalyst turnover number (TON) was accomplished in the cross-metathesis of tetrafluoroethylene (TFE) and vinyl ethers. Under a continuous flow of TFE, catalyst , which contains a seven-membered N-heterocyclic carbene (NHC) ligand, reached a TON of 4100; this is 2 orders of magnitude higher than the highest hitherto reported value. Mechanistic studies revealed that the expanded NHC successfully destabilizes the stable intermediates with a difluorocarbene structure, which strongly promotes the reaction.

Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source.

Fluorinated dialkyl carbonates (DACs), which serve as environmentally benign phosgene substitutes, were produced successfully from carbon dioxide either directly or indirectly. Nucleophilic addition of 2,2,2-trifluoroethanol to carbon dioxide and subsequent reaction with 2,2,2-trifluoroethyltriflate (3 a) afforded bis(2,2,2-trifluoroethyl) carbonate (1) in up to 79 % yield. Additionally, carbonate 1 was obtained through the stoichiometric reaction of 3 a and cesium carbonate.

Visible-Light-Activated Catalytic Enantioselective β-Alkylation of α,β-Unsaturated 2-Acyl Imidazoles Using Hantzsch Esters as Radical Reservoirs.

An efficient and practical method for the enantioselective β-functionalization of α,β-unsaturated 2-acyl imidazoles is described. The method uses a previously devised chiral-at-metal rhodium catalyst (Λ-RhS, 4 mol %) along with Hantzsch ester derivatives as alkyl radical sources. The rhodium complex exerts a dual role as the visible-light-absorbing unit upon substrate binding and as the asymmetric catalyst.

Phosphorescence Resulting from Interaction between Two Non-equivalent Metals on a Helical π-Conjugated Surface.

A [7]helicene bis-ruthenium complex, with one ruthenium atom bound to the cyclopentadienyl (Cp) ring and the other coordinated to the arene ring at the edge of the helicene, was synthesized. This complex showed phosphorescence both in butyronitrile (Φ=31 %, 77 K) and in the solid state (Φ=18 %, 77 K). The two non-equivalent ruthenium metal atoms, attached to the helicene ligand, interact with each other upon photoabsorption and emission.

Synthesis of Optically Pure Helicene Metallocenes.

Two types of ruthenocenes and a ferrocene coordinated by rac-9H-cyclopenta[1,2-c:4,3-c']diphenanthrenyl anion(s), a [7]helicene with a cyclopentadienyl moiety at the center of its skeleton, were successfully synthesized: mono-helicene ruthenocene 1 and its iron analogue 1 with one [7]helicene ligand bound to the central metal, and bis-helicene ruthenocene 2 with two [7]helicenes. Starting from a racemic mixture of the ligand precursor, rac-2 and meso-2 were obtained in a 7:3 ratio. Since the [7]helicene has a high racemization barrier, enantiomers of the complexes were isolated in their pure forms; they showed large optical rotations and intense circular dichroism (CD) responses.

Synthesis and Properties of [7]Helicene-like Compounds Fused with a Fluorene Unit.

[7]Helicene-like compounds with a fluorene unit were successfully synthesized using a platinum-catalyzed double cyclization reaction. Crystal structures and photophysical properties of these compounds were also studied. In particular, they were found to exhibit a high fluorescence quantum yield and a relatively large g value (dissymmetric factor) of circularly polarized luminescence (CPL) for small molecules.

Peptide-catalyzed kinetic resolution of planar-chiral metallocenes.

Kinetic resolution of racemic planar-chiral metallocenes was performed through the conjugate addition of a nucleophile to the enal part of substrates. While no enantiomeric discrimination was found with low-molecular-weight organocatalysts, a properly designed resin-supported peptide catalyzed the reaction in a highly selective manner.

Acceptorless dehydrogenation of C-C single bonds adjacent to functional groups by metal-ligand cooperation.

Unprecedented direct acceptorless dehydrogenation of C-C single bonds adjacent to functional groups to form α,β-unsaturated compounds has been accomplished by using a new class of group 9 metal complexes. Metal-ligand cooperation operated by the hydroxycyclopentadienyl ligand was proposed to play a major role in the catalytic transformation.

Surgical correction of a partial atrioventricular septal defect with a ventricular septal defect in a dog.

Echocardiography of a dog with a cardiac murmur revealed an ostium primum septal defect, a ventricular septal defect, and mitral valve malformation with regurgitation. The mitral valve and tricuspid valve were separated and displaced at the same level as the ventricular septum. The mitral valve had a cleft in the septal cusp.

Implantation of permanent transvenous endocardial pacemaker in a dog with atrioventricular block.

A 10-year old male mongrel dog was presented to the University Veterinary Teaching Hospital with a two-month history of episodic syncope. Twenty-four hr Holter electrocardiographic (ECG) recording revealed frequent episodes of advanced atrioventriculer block with long periods of ventricular asystole. The cause of syncope was determined to be Adams-Stokes syndrome exhibited bradyarrhythmia.