Generalized Weierstrass Relations and Frobenius Reciprocity

This article investigates local properties of the further generalized Weierstrass relations for a spin manifold S immersed in a higher dimensional spin manifold M from the viewpoint of the study of submanifold quantum mechanics. We show that the kernel of a certain Dirac operator defined over S, which we call a submanifold Dirac operator, gives the data of the immersion. In the derivation, the simple Frobenius reciprocity of Clifford algebras S and M plays an important role.      

Protic NNN and NCN Pincer‐Type Ruthenium Complexes Featuring (Trifluoromethyl)pyrazole Arms: Synthesis and Application to Catalytic Hydrogen Evolution from Formic Acid

NNN and NCN pincer‐type ruthenium(II) complexes featuring two protic pyrazol‐3‐yl arms with a trifluoromethyl (CF₃) group at the 5‐position were synthesized and structurally characterized to evaluate the impact of the substitution on the properties and catalysis. The increased Brønsted acidity by the highly electron‐withdrawing CF₃ pendants was demonstrated by protonation–deprotonation experiments. By contrast, the IR spectra of the carbonyl derivatives as well as the cyclic voltammogram indicated that the electron density of the ruthenium atom is negligibly influenced by the CF₃ group. Catalysis of these complexes in the decomposition of formic acid to dihydrogen and carbon dioxide was also examined. The NNN pincer‐type complex 1 a with the CF₃ group exhibited a higher catalytic activity than the tBu‐substituted analogue 1 b . In addition, the bis(CF₃‐pyrazolato) ammine derivative 4 catalyzed the reaction even in the absence of base additives.     

Catalytic asymmetric cyano-ethoxycarbonylation reaction of aldehydes using a YLi3 tris(binaphthoxide) (YLB) complex: mechanism and roles of achiral additives

Full details of a catalytic asymmetric cyano-ethoxycarbonylation reaction promoted by a heterobimetallic YLi3 tris(binaphthoxide) complex (YLB 1), especially mechanistic studies, are described. In the cyanation reaction of aldehydes with ethyl cyanoformate, three achiral additives, H2O, tris(2,6-dimethoxyphenyl)phosphine oxide (3a), and BuLi, were required to achieve high reactivity and enantioselectivity (up to >99% yield and up to 98% ee). The roles of achiral additives and the reaction pathway were investigated in detail. In situ IR analysis revealed that the initiation step to generate LiCN from H2O, BuLi, and ethyl cyanoformate is rather slow. On the basis of mechanistic studies of the initiation step to generate an active nucleophilic species, reaction conditions were optimized by using a catalytic amount of acetone cyanohydrin as an initiator. Under the optimized conditions, the induction period decreased and the reaction completed within 9 min using 5 mol % YLB at -78 degrees C. Catalyst loading was successfully reduced to 1 mol %. Kinetic experiments and evaluation of the substituent effects of phosphine oxide revealed that phosphine oxide had beneficial effects on both the reaction rate and the enantioselectivity. The putative active species as well as the catalytic cycle of the reaction are also discussed.     

Bismuth‐ and Hafnium‐Catalyzed Hydroamination of Vinyl Arenes with Sulfonamides,Carbamates, and Carboxamides

Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)₃/[Cu(CH₃CN)₄]PF₆ system previously developed for catalytic intermolecular hydroamination of 1,3‐dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)₄/[Cu(CH₃CN)₄]PF₆ system was determined to be highly suitable. The combination of Hf(OTf)₄ and [Cu(CH₃CN)₄]PF₆ efficiently promoted the hydroamination of various vinyl arenes, including less‐reactive vinyl arenes with electron‐withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99 % yield with 0.3–10 mol % catalyst loading.     

Stability of lithium in α-rhombohedral boron

The stability of lithium atoms in α-rhombohedral boron was studied by the density functional theory and Car-Parrinello molecular dynamics (MD) simulations. At a low Li concentration (1.03 at%), a Li atom at the center of the icosahedral B₁₂ site (the I-site) was found to be metastable, and the potential barrier was estimated at 775±25 K (=67±25 meV). Over 800 K, Li atoms began to escape from the B₁₂ cage and settled at the tetrahedral site (the T-site) or at the octahedral site (the O-site). Li at the T-site was also metastable below 1400 K, and Li at the O-site was energetically the most favorable. At a high Li concentration (7.69 at%), the I-site changed to an unstable saddle point. The T-site was still metastable, and the O-site was the most stable. Regardless of concentration, MD simulations showed that Li atoms at the O-site never jumped to other sites below 1400 K. The migration of Li would be very slow below this temperature.     

Liquid chromatography/mass spectrometric determination of patulin in apple juice using atmospheric pressure photoionization

This paper describes a comparison between atmospheric pressure chemical ionization (APCI) and the recently introduced atmospheric pressure photoionization (APPI) technique for the liquid chromatography/mass spectrometric (LC/MS) determination of patulin in clear apple juice. A column switching technique for on-line extraction of clear apple juice was developed. The parameters investigated for the optimization of APPI were the ion source parameters fragmentor voltage, capillary voltage, and vaporizer temperature, and also mobile phase composition and flow rate. Furthermore, chemical noise and signal suppression of analyte signals due to sample matrix interference were investigated for both APCI and APPI. The results indicated that APPI provides lower chemical noise and signal suppression in comparison with APCI. The linear range for patulin in apple juice (correlation coefficient >0.999) was 0.2-100 ng mL(-1). Mean recoveries of patulin in three apple juices ranged from 94.5 to 103.2%, and the limit of detection (S/N = 3), repeatability and reproducibility were 1.03-1.50 ng mL(-1), 3.9-5.1% and 7.3-8.2%, respectively. The total analysis time was 10.0 min.     

Shinsonefuran, a cytotoxic furanosesterterpene with a novel carbon skeleton, from the deep-sea sponge Stoeba extensa

Shinsonefuran, a cytotoxic sesterterpene with a novel carbon skeleton, was isolated from the deep-sea sponge Stoeba extensa. The gross structure and relative stereochemistry of shinsonefuran were determined by spectral and chemical methods. In addition, relative stereochemistry of halisulfate 7, previously reported from a marine sponge Coscinoderma sp., was revised. Shinsonefuran exhibited cytotoxicity against HeLa cells with an IC₅₀ value of 16 μg/mL.     

Ytterbium triflate-assisted catalytic oxidative cross-coupling of 2-naphthol derivatives

The oxidative coupling of 2-naphthol and 3-hydroxy-2-naphthoate derivatives with a copper catalyst under an O₂ atmosphere was carried out. The reaction in the presence of a catalytic amount of the Lewis acid, Yb(OTf)₃, proceeded in a cross-coupling specific manner.