Synthesis, π‐Face‐Selective Aggregation,and π‐Face Chiral Recognition of Configurationally Stable C3‐Symmetric Propeller‐Chiral Molecules with a π‐Core

The C₃‐symmetric propeller‐chiral compounds (P,P,P)‐ 1 and (M,M,M)‐ 1 with planar π‐cores perpendicular to the C₃‐axis were synthesized in optically pure states. (P,P,P)‐ 1 possesses two distinguishable propeller‐chiral π‐faces with rims of different heights named the (P/L)‐face and (P/H)‐face. Each face is configurationally stable because of the rigid structure of the helicenes contained in the π‐core. (P,P,P)‐ 1 formed dimeric aggregates in organic solutions as indicated by the results of ¹H NMR, CD, and UV/Vis spectroscopy and vapor pressure osmometry analyses. The (P/L)/(P/L) interactions were observed in the solid state by single‐crystal X‐ray analysis, and they were also predominant over the (P/H)/(P/H) and (P/L)/(P/H) interactions in solution, as indicated by the results of ¹H and 2D NMR spectroscopy analyses. The dimerization constant was obtained for a racemic mixture, which showed that the heterochiral (P,P,P)‐ 1 /(M,M,M)‐ 1 interactions were much weaker than the homochiral (P,P,P)‐ 1 /(P,P,P)‐ 1 interactions. The results indicated that the propeller‐chiral (P/L)‐face interacts with the (P/L)‐face more strongly than with the (P/H)‐face, (M/L)‐face, and (M/H)‐face. The study showed the π‐face‐selective aggregation and π‐face chiral recognition of the configurationally stable propeller‐chiral molecules.     

Nickel-catalyzed intermolecular coupling of 1,3-dienes and aldehydes via transmetalation of nickelacycles with diisobutylaluminum acetylacetonate

Intermolecular coupling reactions of 1,3-dienes and aldehydes via transmetalation of nickelacycle intermediate with (i)Bu(2)Al-acac were investigated. In the reactions, a linear adduct or a branched adduct was produced, depending upon the nature of 1,3-dienes and aldehydes, via two nickelacycles that were relatively stable among the four possible nickelacycles because of the equilibrium with pi-allynickel forms.     

The first halogen-substituted cyclotrigermenes: a unique halogen walk over the three-membered ring skeleton and facial stereoselectivity in the Diels-Alder reaction

Dark red crystals of the halogen-substituted cyclotrigermenes [(tBu3Si)3Ge3X; X = Cl, Br, I] were obtained in good yields by the reaction of [(tBu3Si)3Ge3]+.TTFPB- (TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate) with potassium halides (KCl, KBr, or KI) in diethyl ether. The crystal structures of the halogen-substituted cyclotrigermenes reveal a cis-bent Ge=Ge double bond, caused by the introduction of the electronegative halogen atom on the sp3 germanium atom of cyclotrigermene. In solution, an intramolecular halogen migration over the three-membered ring skeleton was observed. Facial stereoselectivity in the Diels-Alder reaction of new cyclotrigermenes with 2,3-dimethyl-1,3-butadiene is also reported.     

The Effects of Comprehensive Exercise Program on the Adjustments of Standing Balance in Community-Dwelling Elderly Persons

The objective of this study was to assess the effect of comprehensive exercise program widely accepted as a community-based physical intervention for the prevention of falling in the elderly persons on their controlling standing balance. Twenty-six community-dwelling elderly persons (13 males and females; 69.8 ± 2.8 years old) participated in this study. Daily exercise was comprised of walking for more than 30 min, stretching, muscle strengthening and balance exercise without exercise equipments. The intervention was continued for three months. Indicators of standing balance related to static balance, dynamic balance and postural response were measured before and after the intervention. As an effect of the intervention on static balance, the sway of center of pressure (COP) in the static stance significantly increased. In the dynamic balance, significant improvements were observed in one leg standing time, the 10-m gait time, functional reach. Additionally, the maximal movable length of COP which subjects can move voluntarily to right and left significantly increased. In the postural response, the integrated electromyography (IEMG) induced by postural response for sudden postural perturbation significantly decreased in the lower leg muscles. Since less muscular activities were sufficient to maintain posture, it was suggested that postural response was elicited more efficiently following the intervention. This study suggested that the comprehensive exercise program, which has been widely introduced as community-based interventions for the prevention of falling, have extensive effects on the control of standing balance covering static balance, dynamic balance and postural response in the elderly persons.     

A recyclable catalyst for asymmetric transfer hydrogenation with a formic acid-triethylamine mixture in ionic liquid

A novel task-specific ionic ligand with an imidazolium salt moiety was synthesized, and its catalytic ability and recyclability for asymmetric transfer hydrogenation of acetophenone derivatives with a formic acid-triethylamine azeotropic mixture in an ionic liquid [bmim][PF6] was examined.     

Second hyperpolarizabilities (gamma) of bisimidazole and bistriazole benzenes: diradical character, charged state, and spin state dependences

The second hyperpolarizabilities of bisimidazole- and bistriazole-benzene compounds have been calculated at different levels of approximation to unravel the effects of diradical character as well as of charge and spin multiplicity. The largest second hyperpolarizabilities are associated with intermediate diradical character, provided positive charging does not compensate for this effect. For the neutral diradical bisimidazole compound, the singlet diradical species possesses a second hyperpolarizability two to three times larger than the corresponding triplet, demonstrating the possibility of spin state control of the third-order NLO responses for diradical species.     

Nickel‐Promoted Highly Regioselective Carboxylation of Aryl Ynol Ether and Its Application to the Synthesis of Chiral β‐Aryloxypropionic Acid Derivatives

Nickel(0)‐promoted carboxylation of aryl ynol ether proceeded in a highly regioselective manner to produce α‐substituted‐β‐aryloxyacrylic acid derivatives. The α‐substituted‐β‐aryloxyacrylic acids were transformed into the corresponding β‐aryloxypropionic acid derivative as an optically active form via rhodium‐catalyzed asymmetric hydrogenation.