Generation of free radicals at subzero temperatures. III. Polyamine–hydroperoxide–iron system

The mechanism of the reaction of tetraethylenepentamine (TEPA) with cumene hydroperoxide (CHP) and iron ions was investigated. It was found that (1) TEPA did not reduce Fe(III); (2) TEPA was consumed by this reaction; (3) both Fe(II) and Fe(III) were effective for this reaction. It was shown that though the O? O bond of a hydroperoxide could be cleaved only at elevated temperatures, it could be easily cleaved by the reaction with the iron–TEPA complex. The function of this iron–TEPA complex is discussed.     

Selective Encapsulation and Unusual Stabilization of cis-Isomers by a Spherical Polyaromatic Cavity

To explore new cavity functions, we herein employed cis-trans stereoisomers with a N=N, C=C, or C=N unit as guest indicators for a polyaromatic capsule. Thanks to the rigid, spherical cavity with a diameter of ∼1 nm, azobenzene and stilbene derivatives are quantitatively encapsulated by the capsule with 100 % cis-selectivity in water. The isomerization of the cis-azo compound is suppressed against heat and light in the cavity, due to the confinement effect. Furthermore, C,N-diphenyl imine derivatives are quantitatively encapsulated by the capsule in water and adopt an otherwise unstable cis-form. The polyaromatic cavity suppresses the hydrolysis of the imines in water, even at elevated temperature, due to the shielding effect. Accordingly, the properties of the cis-trans isomers could be largely altered through supramolecular manipulation.     

Efficient synthesis of N-nosyl-protected 3-azabicyclo[4.3.0]nonen-8-one by an aniline- and nitrobenzene-mediated Pauson–Khand cyclization

The intramolecular Pauson–Khand cyclization in the presence of both aniline and nitrobenzene was used to improve the construction of N-nitrobenzenesulfonyl-protected 3-azabicyclo[4.3.0]nonane skeletons. We found that aniline enhanced the cyclization and that nitrobenzene prevents the concurrent reduction in this process. This combination of mediators allows for the efficient synthesis of bioactive azabicyclic nonane-type alkaloids and the use of milder deprotection conditions in the synthetic route.     

Risks of Muscle Atrophy in Patients with Malignant Lymphoma after Autologous Stem Cell Transplantation

Objective: Muscle atrophy is associated with autologous stem cell transplantation (ASCT)-related outcomes in patients with malignant lymphoma (ML). However, the impact of ASCT on muscle mass remains unclear in patients with ML. The aims of this study were to investigate changes in muscle mass and risk profiles for muscle atrophy after ASCT. Method: We enrolled 40 patients with refractory ML (age 58 [20-74] years, female/male 16/24, body mass index (BMI) 21.1 kg/m² [17.1-29.6]). Psoas muscle mass was assessed using the psoas muscle index (PMI) before and after ASCT. Statistical analysis used: Independent factors associated with a severe decrease rate of change in PMI were evaluated by decision-tree analysis, respectively. Results: PMI was significantly decreased after ASCT (4.61 vs. 4.55 cm²/m²; P=0.0425). According to the decision-tree analysis, the regimen was selected as the initial split. The rates of change in PMI were −5.57% and −3.97% for patients administered MCEC and LEED, respectively. In patients who were administered LEED, the second branching factor was BMI. In patients with BMI < 20.3 kg/m², the rate of change in PMI was −7.16%. On the other hand, the rate of change in PMI was 4.05% for patients with BMI ≥ 20.3 kg/m². Conclusion: We demonstrated that muscle mass decreased after ASCT in patients with ML. Patients who received MCEC and patients with low BMI were at risk for a decrease in muscle mass.     

Activation and Deactivation of Phillips Catalyst for Ethylene Polymerization Using Various Activators

The present article reveals important roles of metal alkyl activators in tuning the performance of the Phillips catalyst in ethylene polymerization. The addition of aluminum alkyl aids the activation of the catalyst, while excess addition leads to the loss of the activity. The balance between the activation and deactivation depends on the type of employed aluminum alkyl, and tri‐n‐octylaluminum offers the most efficient catalyst usage by preferentially suppressing the deactivation. The passivation of aluminum trialkyl with a hindered phenol mildens not only the deactivation but also chain transfer reactions, leading to an increment of high molecular weight fractions.

     

Cyclic monoterpenes trapped in a polyaromatic capsule: unusual selectivity,isomerization, and volatility suppression

Cyclic monoterpenes (CMTs) are intractable natural products with high volatility and strong odors so that there has been no molecular receptor capable of selectively and tightly trapping CMTs in both solution and the solid state. We herein report that a polyaromatic capsule acts as a functional nanoflask for CMTs with the following five features: (i) the capsule can selectively bind menthone from mixtures with other saturated CMTs in water. In contrast, (ii) treatment of the capsule with mixtures of menthone and π-conjugated CMTs gives rise to ternary host–guest complexes with high pair-selectivity. Notably, (iii) the encapsulated menthone displays unusual isomerization from a typical chair conformer to otherwise unstable conformers upon heating. (iv) The selective binding of volatilized CMTs is demonstrated by the capsule even in the solid state at atmospheric pressure. Furthermore, (v) the volatilities of CMTs are significantly suppressed at elevated temperatures by the capsule upon encapsulation in solution as well as in the solid state.

A polyaromatic capsule demonstrated its unique host functions toward cyclic monoterpenes, i.e., selective binding in water, pair-selective encapsulation, unusual isomerization, selective binding in the solid state, and remarkable volatility suppression.     

Synthetic Design of Carbonyl‐Group‐Containing Compounds Based on C−O Bond Cleavage Promoted by Pd Complexes

On the basis of fundamental studies on elementary processes involving allyl−O and acyl−O bond cleavages, various new catalytic processes to convert carboxylic acid derivatives have been realized. The new processes include 1) carbonylation of allyl formates to β,γ‐unsaturated acids, 2) amination, alkylation, and carbonylation of allylic alcohols, 3) aldehyde synthesis by hydrogenation of carboxylic anhydrides and carboxylic acids, 4) ketone synthesis by combination of the C−O bond cleavage with transmetallation by organoboronic acids. The processes described here have advantages over the conventional ones in that they are more atom‐efficient and halogen‐free in realizing the syntheses of a variety of carbonyl‐containing compounds under mild conditions.     

A Porous Polyaromatic Solid for Vapor Adsorption of Xylene with High Efficiency,Selectivity, and Reusability

Development of porous materials capable of capturing volatile organic compounds (VOCs), such as benzene and its derivatives, with high efficiency, selectivity, and reusability is highly demanded. Here we report unusual vapor adsorption behavior toward VOCs by a new porous solid, composed of a polyaromatic capsule bearing a spherical nanocavity with subnano-sized windows. Without prior crystallization and high-temperature vacuum drying, the porous polyaromatic solid exhibits the following five features: vapor adsorption of benzene over cyclohexane with 90 % selectivity, high affinity toward o-xylene over benzene and toluene with >80 % selectivity, ortho-selective adsorption ability (>50 %) from mixed xylene isomers, tight VOCs storage even under high temperature and vacuum conditions, and at least 5 times reusability for xylene adsorption. The observed adsorption abilities are accomplished at ambient temperature and pressure within 1 h, which has not been demonstrated by organic/inorganic porous materials reported previously.