Indole and its derivatives represent the most important heterocycles that are widely present in bioactive molecules,natural products and advanced materials,and thus functionalization of simple indoles to construct com...Indole and its derivatives represent the most important heterocycles that are widely present in bioactive molecules,natural products and advanced materials,and thus functionalization of simple indoles to construct complex indole derivatives is a research area of great current interest.2,3-Difunctionalization of indoles has been extensively studied,but the reported examples are limited to the synthesis of 2,3-disubstituted indole derivatives or dearomatized products containing central chirality.Until now,atroposelective 2,3-difunctionalization of simple indoles for the synthesis of axially chiral molecules is unknown.In this article,we report a straightforward and general strategy for atroposelective 2,3-difunctionalization of simple indoles,forming indole-containing axially chiral products in good yields and excellent enantioselectivities.The strategy we introduce herein may lead to the discovery of new approaches for multifunctionalization of indoles and other heterocyclic scaffolds,thus accessing novel axially chiral heteroarene-containing scaffolds that may find applications in medicinal chemistry and asymmetric catalysis.展开更多
Despite rapid development in the past two decades,there are still some unsolved synthetic challenges in the field of phosphine catalysis.In this report,through photo-induced activation of ortho-alkyl aromatic ketones,...Despite rapid development in the past two decades,there are still some unsolved synthetic challenges in the field of phosphine catalysis.In this report,through photo-induced activation of ortho-alkyl aromatic ketones,we achieved highly enantioselective functionalization of substrates bearing a benzylic C–H bond.In the presence of amino acid-derived bifunctional phosphine catalysts,a range of benzylic allylation products were obtained in good yields and with excellent enantioselectivities.The strategy disclosed herein offers new insight into the activation and functionalization of pronucleophiles containing less acidic C–H bonds in the domain of phosphine catalysis and beyond.展开更多
Biomaterials with suitable osteoimmunomodulation properties and ability to deliver osteoinductive biomolecules,such as bone morphogenetic proteins,are desired for bone regeneration.Herein,we report the development of ...Biomaterials with suitable osteoimmunomodulation properties and ability to deliver osteoinductive biomolecules,such as bone morphogenetic proteins,are desired for bone regeneration.Herein,we report the development of mesoporous silica rods with large cone-shaped pores(MSR-CP)to load and deliver large protein drugs.It is noted that those cone-shaped pores on the surface modulated the immune response and reduced the pro-inflammatory reaction of stimulated macrophage.Furthermore,bone morphogenetic proteins 2(BMP-2)loaded MSR-CP facilitated osteogenic differentiation and promoted osteogenesis of bone marrow stromal cells.In vivo tests confirmed BMP-2 loaded MSR-CP improved the bone regeneration performance.This study provides a potential strategy for the design of drug delivery systems for bone regeneration.展开更多
As a kind of important demand side resource,the thermostatically controlled loads(TCLs)play an important role in the peak load shifting and load balancing programs.This paper establishes a state-queuing(SQ)model for t...As a kind of important demand side resource,the thermostatically controlled loads(TCLs)play an important role in the peak load shifting and load balancing programs.This paper establishes a state-queuing(SQ)model for the large-scale TCLs,and estimates the system states based on the Kalman-filtering.Based on state estimation,the control strategy,whose parameters are optimized by the genetic algorithm(GA),is designed to damp the power fluctuation of the TCLs.Finally,the effectiveness of the proposed method is verified.展开更多
文摘Indole and its derivatives represent the most important heterocycles that are widely present in bioactive molecules,natural products and advanced materials,and thus functionalization of simple indoles to construct complex indole derivatives is a research area of great current interest.2,3-Difunctionalization of indoles has been extensively studied,but the reported examples are limited to the synthesis of 2,3-disubstituted indole derivatives or dearomatized products containing central chirality.Until now,atroposelective 2,3-difunctionalization of simple indoles for the synthesis of axially chiral molecules is unknown.In this article,we report a straightforward and general strategy for atroposelective 2,3-difunctionalization of simple indoles,forming indole-containing axially chiral products in good yields and excellent enantioselectivities.The strategy we introduce herein may lead to the discovery of new approaches for multifunctionalization of indoles and other heterocyclic scaffolds,thus accessing novel axially chiral heteroarene-containing scaffolds that may find applications in medicinal chemistry and asymmetric catalysis.
基金supported by the Singapore National Research Foundation,Prime Minister’s Office for the NRF Investigatorship Award(A-0004067-00-02)the Ministry of Education(MOE)of Singapore(A-0008481-00-00)。
文摘Despite rapid development in the past two decades,there are still some unsolved synthetic challenges in the field of phosphine catalysis.In this report,through photo-induced activation of ortho-alkyl aromatic ketones,we achieved highly enantioselective functionalization of substrates bearing a benzylic C–H bond.In the presence of amino acid-derived bifunctional phosphine catalysts,a range of benzylic allylation products were obtained in good yields and with excellent enantioselectivities.The strategy disclosed herein offers new insight into the activation and functionalization of pronucleophiles containing less acidic C–H bonds in the domain of phosphine catalysis and beyond.
基金The authors acknowledge the support from UQ Early Career Researcher Grant(1717673)the National Natural Science Foundation of China(Nos.81871503 and 81701032)+2 种基金C.X.acknowledges the support of National Health&Medical Research Council of Australia(NHMRC)Early Career FellowshipY.H.,L.X.and C.L.extended their appreciations to the support of Advanced QueenslandThe authors acknowledge the support from the Australian Microscopy and Microanalysis Research Facility at the Centre for Microscopy and Microanalysis,the University of Queensland.
文摘Biomaterials with suitable osteoimmunomodulation properties and ability to deliver osteoinductive biomolecules,such as bone morphogenetic proteins,are desired for bone regeneration.Herein,we report the development of mesoporous silica rods with large cone-shaped pores(MSR-CP)to load and deliver large protein drugs.It is noted that those cone-shaped pores on the surface modulated the immune response and reduced the pro-inflammatory reaction of stimulated macrophage.Furthermore,bone morphogenetic proteins 2(BMP-2)loaded MSR-CP facilitated osteogenic differentiation and promoted osteogenesis of bone marrow stromal cells.In vivo tests confirmed BMP-2 loaded MSR-CP improved the bone regeneration performance.This study provides a potential strategy for the design of drug delivery systems for bone regeneration.
基金This work was partially supported by National Natural Science Foundation of China(51707099)University Science Research Project of Jiangsu Province(16KJB470009)China Postdoctoral Science Foundation(2017M611859).
文摘As a kind of important demand side resource,the thermostatically controlled loads(TCLs)play an important role in the peak load shifting and load balancing programs.This paper establishes a state-queuing(SQ)model for the large-scale TCLs,and estimates the system states based on the Kalman-filtering.Based on state estimation,the control strategy,whose parameters are optimized by the genetic algorithm(GA),is designed to damp the power fluctuation of the TCLs.Finally,the effectiveness of the proposed method is verified.
