The development of catalytic asymmetric radical reactions is an attractive but formidable task.The high reactivity of radicals enables the use of readily accessible feedstocks and mild reaction conditions,but it leads...The development of catalytic asymmetric radical reactions is an attractive but formidable task.The high reactivity of radicals enables the use of readily accessible feedstocks and mild reaction conditions,but it leads to substantial difficulty for chiral catalysts to provide sufficient enantiocontrol.Moreover,a racemic background process is often inevitable,further deteriorating enantioselectivity.In this regard,an effective protocol has been established for enantioselective intermolecular[2+2]photocycloadditions to overcome the challenges,which is capitalising on the ground-state preassociations of chiral catalysts with photoactivated substrates.Here,we report the viability of substrate-differentiating synergistic catalysis for this important reaction.In this new platform,energy transfer occurs between DPZ as a photosensitizer and enones or(E)-2-substituted vinylazaarenes for producing triplet-state species,and chiral phosphoric acid interacts with ground-state 2-vinylazaarenes via hydrogen bonding for subsequent enantiofacial cycloaddition.Although all active species are dispersed in the reaction system,valuable enantioenriched mono-and di-azaarene-functionalized cyclobutanes are obtained efficiently and selectively.In addition to constructing all-carbon quaternary stereocentres,flexible modulation of azaaryl groups and other substituents on the cyclobutane ring is also operative.展开更多
The default fractional vegetation cover and terrain height were replaced by the estimated fractional vegetation cover, which was calculated by the Normalized Difference Vegetation Index （NDVI） of Earth Observing Sys...The default fractional vegetation cover and terrain height were replaced by the estimated fractional vegetation cover, which was calculated by the Normalized Difference Vegetation Index （NDVI） of Earth Observing System Moderate-Resolution Im- aging Spectroradiometer （EOS-MODIS） and the Digital Elevation Model of the Shuttle Radar Topography Mission （SRTM） system. The near-surface meteorological elements over northeastern China were assimilated into the three-dimensional varia- tional data assimilation system （3DVar） module in the Weather Research and Forecasting （WRF） model. The structure and daily variations of air temperature, humidity, wind and energy fields over northeastern China were simulated using the WRF model. Four groups of numerical experiments were performed, and the simulation results were analyzed of latent heat flux, sensible heat flux, and their relationships with changes in the surface energy flux due to soil moisture and precipitation over different surfaces. The simulations were compared with observations of the stations Tongyu, Naiman, Jinzhou, and Miyun from June to August, 2009. The results showed that the WRF model achieves high-quality simulations of the diurnal charac- teristics of the surface layer temperature, wind direction, net radiation, sensible heat flux, and latent heat flux over semiarid northeastern China in the summer. The simulated near-surface temperature, relative humidity, and wind speed were improved in the data assimilation case （Case 2） compared with control case （Case 1）. The simulated sensible heat fluxes and surface heat fluxes were improved by the land surface parameterization case （Case 3） and the combined case （Case 4）. The simulated tem- poral variations in soil moisture over the northeastern arid areas agree well with observations in Case 4, but the simulated pre- cipitation should be improved in the WRF model. This study could improve the land surface parameters by utilizing remote sensing data and could further improve atmospheric elements with a data assimilation system. This work provides an effective attempt at combining multi-source data with different spatial and temporal scales into numerical simulations. The assimilation datasets generated by this work can be applied to research on climate change and environmental monitoring of add lands, as well as research on the formation and stability of climate over semiarid areas.展开更多
文摘The development of catalytic asymmetric radical reactions is an attractive but formidable task.The high reactivity of radicals enables the use of readily accessible feedstocks and mild reaction conditions,but it leads to substantial difficulty for chiral catalysts to provide sufficient enantiocontrol.Moreover,a racemic background process is often inevitable,further deteriorating enantioselectivity.In this regard,an effective protocol has been established for enantioselective intermolecular[2+2]photocycloadditions to overcome the challenges,which is capitalising on the ground-state preassociations of chiral catalysts with photoactivated substrates.Here,we report the viability of substrate-differentiating synergistic catalysis for this important reaction.In this new platform,energy transfer occurs between DPZ as a photosensitizer and enones or(E)-2-substituted vinylazaarenes for producing triplet-state species,and chiral phosphoric acid interacts with ground-state 2-vinylazaarenes via hydrogen bonding for subsequent enantiofacial cycloaddition.Although all active species are dispersed in the reaction system,valuable enantioenriched mono-and di-azaarene-functionalized cyclobutanes are obtained efficiently and selectively.In addition to constructing all-carbon quaternary stereocentres,flexible modulation of azaaryl groups and other substituents on the cyclobutane ring is also operative.
基金supported by the National Basic Research Program of China(Grant No.2010CB950504)the National High-tech R&D Program of China(Grant No.2013AA122003)the open funds of the Key Laboratory of Land Surface Process and Climate Change in Cold and Arid Regions,Chinese Academy of Sciences(Grant No.LPCC201101)
文摘The default fractional vegetation cover and terrain height were replaced by the estimated fractional vegetation cover, which was calculated by the Normalized Difference Vegetation Index （NDVI） of Earth Observing System Moderate-Resolution Im- aging Spectroradiometer （EOS-MODIS） and the Digital Elevation Model of the Shuttle Radar Topography Mission （SRTM） system. The near-surface meteorological elements over northeastern China were assimilated into the three-dimensional varia- tional data assimilation system （3DVar） module in the Weather Research and Forecasting （WRF） model. The structure and daily variations of air temperature, humidity, wind and energy fields over northeastern China were simulated using the WRF model. Four groups of numerical experiments were performed, and the simulation results were analyzed of latent heat flux, sensible heat flux, and their relationships with changes in the surface energy flux due to soil moisture and precipitation over different surfaces. The simulations were compared with observations of the stations Tongyu, Naiman, Jinzhou, and Miyun from June to August, 2009. The results showed that the WRF model achieves high-quality simulations of the diurnal charac- teristics of the surface layer temperature, wind direction, net radiation, sensible heat flux, and latent heat flux over semiarid northeastern China in the summer. The simulated near-surface temperature, relative humidity, and wind speed were improved in the data assimilation case （Case 2） compared with control case （Case 1）. The simulated sensible heat fluxes and surface heat fluxes were improved by the land surface parameterization case （Case 3） and the combined case （Case 4）. The simulated tem- poral variations in soil moisture over the northeastern arid areas agree well with observations in Case 4, but the simulated pre- cipitation should be improved in the WRF model. This study could improve the land surface parameters by utilizing remote sensing data and could further improve atmospheric elements with a data assimilation system. This work provides an effective attempt at combining multi-source data with different spatial and temporal scales into numerical simulations. The assimilation datasets generated by this work can be applied to research on climate change and environmental monitoring of add lands, as well as research on the formation and stability of climate over semiarid areas.
