Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and am...Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and amino acids.However,the complexity of multistep reaction routes and the presence of competing side reactions pose significant challenges,often leading to low yield and poor selectivity of target products.To substantially enhance the efficiency and selectivity of C-N coupling reactions,it is imperative to gain a thorough understanding of the underlying reaction mechanisms and to develop highly active photocatalysts.Such catalysts must be capable of effectively activating diverse substrates while maintaining an appropriate balance between the adsorption and desorption of carbon-and nitrogen-containing intermediates or radical species.In this review,we systematically summarize recent advances in photocatalytic C-N coupling for the production of amides and amino acids from waste plastic-and biomass-based feedstocks,with particular focus on catalyst selection,process design,control of reaction intermediates,and catalytic mechanisms.Furthermore,the technoeconomic feasibility and environmental impact of these C-N coupling reactions are evaluated using technoeconomic analysis and life-cycle assessment.Lastly,the current challenges and future prospects in this field are also discussed.This review aims to provide valuable insights for the development of high-efficiency photocatalytic C-N coupling reactions and to deepen the understanding of their catalytic mechanisms.展开更多
Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as pre...Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22572141,22178266)Talent Program Fund of Tianjin University(Nos.0701321039,0903074107)supported by a grant from the Key Laboratory of Recycling and Eco-Treatment of Waste Biomass of Zhejiang Province(No.2024HZYB02)。
文摘Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and amino acids.However,the complexity of multistep reaction routes and the presence of competing side reactions pose significant challenges,often leading to low yield and poor selectivity of target products.To substantially enhance the efficiency and selectivity of C-N coupling reactions,it is imperative to gain a thorough understanding of the underlying reaction mechanisms and to develop highly active photocatalysts.Such catalysts must be capable of effectively activating diverse substrates while maintaining an appropriate balance between the adsorption and desorption of carbon-and nitrogen-containing intermediates or radical species.In this review,we systematically summarize recent advances in photocatalytic C-N coupling for the production of amides and amino acids from waste plastic-and biomass-based feedstocks,with particular focus on catalyst selection,process design,control of reaction intermediates,and catalytic mechanisms.Furthermore,the technoeconomic feasibility and environmental impact of these C-N coupling reactions are evaluated using technoeconomic analysis and life-cycle assessment.Lastly,the current challenges and future prospects in this field are also discussed.This review aims to provide valuable insights for the development of high-efficiency photocatalytic C-N coupling reactions and to deepen the understanding of their catalytic mechanisms.
基金supported by the National Natural Sci-ence Foundation of China(Nos.22478263,22308230)Natural Science Foundation of Sichuan(No.2024NSF-SC1134)+2 种基金China Postdoctoral Science Foundation(No.2024T170612)111 center(B17030)the Fun-damental Research Funds for the Central Universities.
文摘Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.
