Asymmetric Epoxidation of 1,4-Naphthoquinones Catalyzed by Guanidine-Urea Bifunctional Organocatalyst.

An enantioselective nucleophilic epoxidation of 2-substituted 1,4-naphthoquinones in the presence of a newly developed guanidine-bisurea bifunctional organocatalyst with tert-butyl hydroperoxide (TBHP) as an oxidant is presented. 1,4-Naphthoquinones bearing substituents at C6, C7, and C2 were available for the reaction, and the corresponding epoxides were obtained with 88:12-95:5 er in 71-98% yields. DFT calculations indicated that substituents at C2 and C6 in the terminal Ar group of the catalyst 9k play a key role in controlling the stereochemical outcome.

The effects of future nationwide forest transition to discharge in the 21st century with regard to general circulation model climate change scenarios.

Forest disturbance (or land-cover change) and climatic variability are commonly recognised as two major drivers interactively influencing hydrology in forested watersheds. Future climate changes and corresponding changes in forest type and distribution are expected to generate changes in rainfall runoff that pose a threat to river catchments. It is therefore important to understand how future climate changes will effect average rainfall distribution and temperature and what effect this will have upon forest types across Japan. Recent deforestation of the present-day coniferous forest and expected increases in evergreen forest are shown to influence runoff processes and, therefore, to influence future runoff conditions. We strongly recommend that variations in forest type be considered in future plans to ameliorate projected climate changes. This will help to improve water retention and storage capacities, enhance the flood protection function of forests, and improve human health. We qualitatively assessed future changes in runoff including the effects of variation in forest type across Japan. Four general circulation models (GCMs) were selected from the Coupled Model Intercomparison Project Phase 5 (CMIP5) ensemble to provide the driving fields: the Model for Interdisciplinary Research on Climate (MIROC), the Meteorological Research Institute Atmospheric General Circulation Model (MRI-GCM), the Hadley Centre Global Environment Model (HadGEM), and the Geophysical Fluid Dynamics Laboratory (GFDL) climate model. The simulations consisted of an ensemble including multiple physics configurations and different reference concentration pathways (RCP2.6, 4.5, and 8.5), the results of which have produced monthly data sets for the whole of Japan. The impacts of future climate changes on forest type in Japan are based on the balance amongst changes in rainfall distribution, temperature and hydrological factors. Methods for assessing the impact of such changes include the Catchment Simulator modelling frameworks based on the Minimal Advanced Treatments of Surface Interaction and Runoff (MATSIRO) model, which was expanded to estimate discharge by incorporating the effects of forest-type transition across the whole of Japan. The results indicated that, by the 2090s, annual runoff will increase above present-day values. Increases in annual variation in runoff by the 2090s was predicted to be around 14.1% when using the MRI-GCM data and 44.4% when using the HadGEM data. Analysis by long-term projection showed the largest increases in runoff in the 2090s were related to the type of forest, such as evergreen. Increased runoff can have negative effects on both society and the environment, including increased flooding events, worsened water quality, habitat destruction and changes to the forest moisture-retaining function. Prediction of the impacts of future climate change on water generation is crucial for effective environmental planning and management.

Entropy-Driven 1,2-Type Friedel-Crafts Reaction of Phenols with N-tert-Butoxycarbonyl Aldimines.

Differential activation entropy (ΔΔS(≠)) is revisited as an important parameter that governs catalytic stereodiscrimination processes by investigating temperature effects on the basis of the Eyring theory. However, correlating the ΔΔS(≠) effect and the molecular structure of the asymmetric catalyst is still an underdeveloped area. Efforts to identify factors (including catalyst structure, reactants, and reaction conditions) that contribute to the attainment of large ΔΔS(≠) values for enantioselective 1,2-type Friedel-Crafts reactions of phenols with N-tert-butoxycarbonyl aldimines catalyzed by conformationally flexible guanidine bisthioureas are described. First, we uncover an interesting property of the ΔΔS(≠)-driven stereodiscrimination process: maximum enantioselectivity is obtained at around room temperature. Second, a plausible transition-state model accounting for the characteristic ΔΔS(≠) effect and the structural dynamics of the conformationally flexible organocatalyst in the stereodiscrimination process is discussed.

Conical intersections of free energy surfaces in solution: effect of electron correlation on a protonated Schiff base in methanol solution.

The minimum energy conical intersection (MECI) optimization method with taking account of the dynamic electron correlation effect [T. Mori and S. Kato, Chem. Phys. Lett. 476, 97 (2009)] is extended to locate the MECI of nonequilibrium free energy surfaces in solution. A multistate electronic perturbation theory is introduced into the nonequilibrium free energy formula, which is defined as a function of solute and solvation coordinates. The analytical free energy gradient and interstate coupling vectors are derived, and are applied to locate MECIs in solution. The present method is applied to study the cis-trans photoisomerization reaction of a protonated Schiff base molecule (PSB3) in methanol (MeOH) solution. It is found that the effect of dynamic electron correlation largely lowers the energy of S(1) state. We also show that the solvation effect strongly stabilizes the MECI obtained by twisting the terminal C=N bond to become accessible in MeOH solution, whereas the conical intersection is found to be unstable in gas phase. The present study indicates that both electron correlation and solvation effects are important in the photoisomerization reaction of PSB3. The effect of counterion is also examined, and seems to be rather small in solution. The structures of free energy surfaces around MECIs are also discussed.