Chiral ruthenabicyclic complexes: precatalysts for rapid, enantioselective, and wide-scope hydrogenation of ketones

A novel ruthenabicyclic complex with base shows excellent catalytic activity in the asymmetric hydrogenation of ketones. The turnover frequency of the hydrogenation of acetophenone reaches about 35,000 min(-1) in the best case, affording 1-phenylethanol in >99% ee. Several aliphatic and base-labile ketones are smoothly converted to the corresponding alcohols in high enantioselectivity. The catalytic cycle for this hydrogenation, in which the ruthenabicyclic structure of the catalyst is maintained, is proposed on the basis of the deuteration experiment and spectroscopic analysis data.     

A kinetically stabilized ferrocenyl diphosphene: synthesis, structure, properties, and redox behavior

A new, stable ferrocenyl diphosphene [Tbt-P==P-Fc] (1) (Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Fc = ferrocenyl) was synthesized by the dehydrochlorination reaction of the corresponding diphosphane, [Tbt-P(H)-P(Cl)-Fc] (8), with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in good yield. Diphosphene 1 is very stable in the solid state and also in solution. In the 31P NMR spectrum (C6D6), diphosphene 1 showed a low-fielded AB quartet at delta 501.7 and 479.5 ppm with the coupling constant 1J(PP)=546 Hz, which is characteristic of an unsymmetrically substituted trans-diphosphene. The molecular structure of 1 was established by X-ray crystallographic analysis, which showed a trans-diphosphene with a C-P-P-C torsion angle of 177.86(17) degrees . The phosphorus-phosphorus bond length of 1 [2.0285(15) A] which is considerably shorter than the typical P-P single-bond lengths (ca. 2.22-2.24 A) and within the range of reported P=P double-bond lengths (1.985-2.051 A) for diaryl diphosphenes, evidenced the P=P double-bond character of 1 in the solid state. In addition, the cyclic voltammograms of 1 showed reversible reduction and oxidation couples at -1.95 and +0.34 V versus SCE, respectively. The electrochemical results for 1 were reasonably supported by the DFT calculations, which suggested that the LUMO and HOMO orbitals should be mainly pi* orbital of the diphosphene moiety and d orbitals of the iron(II) atom, respectively.     

Design and evaluation of imidazolium cation-based ionic liquids having double-armed anions for selective cation conduction

A series of triple ionic compounds consisting of double armed anions and one cation were prepared as lithium cation conductive matrices. As anions, lithium borates derived from lithium-9-borabicyclo[3,3,1]nonane hydride were introduced. The sterically hindered borate anion structures prevented the crystallization of triple ionic compounds. Introduction of ethylene oxide chains attached to the borate anions led to lower glass transition temperature, and also improved ionic conductivity. A lithium transference number of 0.73 was observed in spite of the presence of ethylene oxide chains.     

A Potassium Complex of a Fluorine-Containing Macrocyclic Cage Compound: Interactions between Fluorine Atoms and Metal Ions

A new donor , the C−F unit, can be added to the field of host–guest chemistry. The interaction between fluorine atoms and a potassium ion was proven with the fluorine-containing cage compound 1 as a host. The six fluorine atoms of K⁺⊂ 1 are coordinated to K⁺ in a distorted octahedral fashion.     

Enantioselective Ring Opening of Epoxides with 4-Methoxyphenol Catalyzed by Gallium Heterobimetallic Complexes: An Efficient Method for the Synthesis of Optically Active 1,2-Diol Monoethers

Useful chiral building blocks such as 1,2-diols can be obtained by the enantioselective ring opening of achiral epoxides with oxygen nucleophiles. The ring opening is carried out effectively (up to 94 % ee) with 4-methoxyphenol and catalytic amounts of gallium complexes. The novel complex GaSO 1 displays a particularly high catalytic activity.     

Initiation gait variability is higher in the morning in elderly inpatients

Objective: Although elderly inpatients are known to experience decreased physical activity in the morning, falls occur frequently during this time. Gait variability is an evaluation of gait instability and a risk factor for falls. Gait initiation requires complex processes, and it is important to evaluate gait variability not only during steady-state gait but also during gait initiation. However, the effect of the diurnal pattern on variability in gait characteristics is still unknown. The aim of this study was to investigate the effect of the diurnal pattern on initiation and steady-state gait variability in elderly inpatients. Method: Thirty-seven elderly inpatients (28 women; mean age, 79.7 ± 9.5 years) who could walk without support were sampled in this study. The quantitative measure of gait variability was evaluated using the coefficient of variation (CV) based on four consecutive stride durations determined using triaxial accelerometers. Gait characteristics were evaluated during initiation and steady-state gait and defined as initiation CV and steady-state CV, respectively. This measurement was performed at two time points, morning and daytime. Results: There was no significant difference between initiation and steady-state gait characteristics in the daytime condition. However, in the morning condition, the initiation CV was higher than the steady-state CV. Furthermore, the initiation CV was higher in the morning than during daytime (p < 0.01). Conclusion: Our study revealed that the variability of initiation gait is higher in the morning. It may be important to assess the risk of falls, including initiation gait, in the morning.     

Inclusion behavior of water-soluble thiacalix- and calix[4]arenes towards substituted benzenes in aqueous solution

Inclusion abilities of thiacalix- and calix[4]arenetetrasulfonate (3 and 4) towards mono-substituted benzenes were investigated in neutral aqueous solution. In general, the hosts regioselectively encapsulated the guests from the aromatic moiety except the complexation of toluene by 4, in which the guest penetrated from either the aromatic or the methyl group. Stabilities of the inclusion complexes increased with the electron-withdrawing ability of the substituent on the guest, suggesting pi-pi electronic interaction between the host and guest. In spite of the lower electron density of the aromatic ring, thiacalix[4]arene 3 showed higher inclusion ability than calix[4]arene 4, suggesting that the size rather than the electron density of the calix framework is a more important factor in determining the inclusion ability.     

Photosensitized intramolecular cyclization of furan and non-activated alkene: pathway switching by the substituent on the furan ring

A photosensitized reaction of furan with a non-activated simple alkene was investigated. Intramolecular Diels-Alder-type cycloaddition reactions between furan and a trisubstituted alkene were found to proceed in high yield in the presence of 9,10-dicyanoanthracene under UV irradiation to afford oxabicyclo[2.2.1]heptane derivatives in high stereoselectivity when the furan was alkyl substituted. On the other hand, the aryl-substituted furan cyclized via a completely different pathway to give spirocyclic and tricyclic products.