1.Introduction The past few decades have witnessed extensive studies on transition metal-catalyzed C-H bond activations and subsequent carbon-carbon and/or carbon-heteroatom bond formations because these methods provi...1.Introduction The past few decades have witnessed extensive studies on transition metal-catalyzed C-H bond activations and subsequent carbon-carbon and/or carbon-heteroatom bond formations because these methods provide more atom-and step-economical pathways than those traditional transformations starting from prefunctionalized substrates.展开更多
Control of enantioselectivity in radical reactions was a formidable challenge for organic chemists for decades. Thanks to the key role of transition metal complexes both in promoting and highly enantioselectively cont...Control of enantioselectivity in radical reactions was a formidable challenge for organic chemists for decades. Thanks to the key role of transition metal complexes both in promoting and highly enantioselectively controlling sophisticated synthetic routes, great improvements in this filed have been achieved by merging transition-metal asymmetric catalysis with radical chemistry. Herein we provide a perspective of some of the most significant contributions in the field during the past decades. Accordingly, the major advances are classified based on different strategies for controlling stereoselectivity including: (1) chiral metal complex chelation, (2) chiral metal complex combined with radical species and reductive elimination, (3) chiral metal complex outer-sphere substitution by radical intermediate. Brief discussion of mechanism is presented whenever relevant.展开更多
Large-scale In2O3 nanotowers with different cross sections were synthesized by a thermal evaporation and oxidation technique using metal as the catalyst. The morphologies and structural characterizations of In2O3 nano...Large-scale In2O3 nanotowers with different cross sections were synthesized by a thermal evaporation and oxidation technique using metal as the catalyst. The morphologies and structural characterizations of In2O3 nanotowers are dependent on growth processes, such as different metal (Au, Ag or Sn) catalysts, the relative position of the substrate and evaporation source, growth temperature, gas flow rate, and growth time. In2O3 nanotowers cannot be observed using Sn as the catalyst, which indicates that metal liquid droplets play an important role in the initial stages of the growth of In2O3 nanotowers. The formation of an In2O3 nanotower is attributed to the competitive growth model between a lateral growth controlled by vapor-solid mechanism and an axial vaporliquid-solid growth mechanism mediated by metal liquid nanodroplets. The synthesized In2O3 nanostructures with novel tower-shaped morphology may have potential applications in optoelectronic devices and gas sensors.展开更多
Cu-catalyzed oxidation of 5-hexyl-1,3-dihydroimidazo-2-one (1) in the presence of propylamine, as surrogates for the oxidized His side chain and Lys side chain, was investigated. 5-Hexylidene-4-propylamino-1,5-dihydro...Cu-catalyzed oxidation of 5-hexyl-1,3-dihydroimidazo-2-one (1) in the presence of propylamine, as surrogates for the oxidized His side chain and Lys side chain, was investigated. 5-Hexylidene-4-propylamino-1,5-dihydroimidazol-2-one (2), a model His-Lys cross-link product, was isolated and structurally characterized by NMR and mass spectrometry.展开更多
A deuterated methylthiolating reagent with a broad spectrum,designated as DMTp,has been ingeniously formulated.This new reagent can be produced with high efficiency through the simple combination of commercially avail...A deuterated methylthiolating reagent with a broad spectrum,designated as DMTp,has been ingeniously formulated.This new reagent can be produced with high efficiency through the simple combination of commercially available methyl 3-thiopropanoate and CD_(3)l.This novel SCD_(3) reagent exhibits excellent reactivity with electrophiles such as alkyl iodides,benzyl chlorides,aryl halides(l,Br)and aryl triflates,resulting in high levels of deuterium content(99%D).Representative deuterated methylthiolated biomolecules,such as Sulfoxaflor,havebeen synthesizedforuse in pharmaceutical discoveryand development.展开更多
α-Olefins as aliphatic terminal alkenes could be obtained easily from numerous contemporary synthetic reactions as well as petro-chemical industry,and also found in natural products.Compared to the alkenes attaching ...α-Olefins as aliphatic terminal alkenes could be obtained easily from numerous contemporary synthetic reactions as well as petro-chemical industry,and also found in natural products.Compared to the alkenes attaching the directing groups or activating group,the catalytic asymmetric reaction of unactivated terminal alkenes presents great challenges due to the weak electron effect and small steric hindrance effect.This review mainly summarizes the latest progress of the asymmetric reaction of unactivated terminal olefins since 2016.展开更多
基金We thank the National Natural Science Foundation of China (Nos. 21871145, 21672107 and 91856104) for financial support.
文摘1.Introduction The past few decades have witnessed extensive studies on transition metal-catalyzed C-H bond activations and subsequent carbon-carbon and/or carbon-heteroatom bond formations because these methods provide more atom-and step-economical pathways than those traditional transformations starting from prefunctionalized substrates.
基金Acknowledgement Financial support from the "1000-Youth Talents Plan" and the National Natural Science Foundation of China (No. 21702149)is greatly appreciated.
文摘Control of enantioselectivity in radical reactions was a formidable challenge for organic chemists for decades. Thanks to the key role of transition metal complexes both in promoting and highly enantioselectively controlling sophisticated synthetic routes, great improvements in this filed have been achieved by merging transition-metal asymmetric catalysis with radical chemistry. Herein we provide a perspective of some of the most significant contributions in the field during the past decades. Accordingly, the major advances are classified based on different strategies for controlling stereoselectivity including: (1) chiral metal complex chelation, (2) chiral metal complex combined with radical species and reductive elimination, (3) chiral metal complex outer-sphere substitution by radical intermediate. Brief discussion of mechanism is presented whenever relevant.
基金supported by the National Natural Science Foundation of China(No.61076055)the Open Project Program of Surface Physics Laboratory(National Key Laboratory)of Fudan University(No.KF2015_02)+1 种基金the Zhejiang Provincial Science and Technology Key Innovation Team(No.2011R50012)the Zhejiang Provincial Key Laboratory(No.2013E10022)
文摘Large-scale In2O3 nanotowers with different cross sections were synthesized by a thermal evaporation and oxidation technique using metal as the catalyst. The morphologies and structural characterizations of In2O3 nanotowers are dependent on growth processes, such as different metal (Au, Ag or Sn) catalysts, the relative position of the substrate and evaporation source, growth temperature, gas flow rate, and growth time. In2O3 nanotowers cannot be observed using Sn as the catalyst, which indicates that metal liquid droplets play an important role in the initial stages of the growth of In2O3 nanotowers. The formation of an In2O3 nanotower is attributed to the competitive growth model between a lateral growth controlled by vapor-solid mechanism and an axial vaporliquid-solid growth mechanism mediated by metal liquid nanodroplets. The synthesized In2O3 nanostructures with novel tower-shaped morphology may have potential applications in optoelectronic devices and gas sensors.
文摘Cu-catalyzed oxidation of 5-hexyl-1,3-dihydroimidazo-2-one (1) in the presence of propylamine, as surrogates for the oxidized His side chain and Lys side chain, was investigated. 5-Hexylidene-4-propylamino-1,5-dihydroimidazol-2-one (2), a model His-Lys cross-link product, was isolated and structurally characterized by NMR and mass spectrometry.
基金financial support from the National Natural Science Foundation of China(22101005)the National Key Research and Development Program of China(2021YFD1700104)+1 种基金Key R&D Projects of Anhui Province(202104a06020008)Excellent Youth Program of Anhui Province(2022AH030095).
文摘A deuterated methylthiolating reagent with a broad spectrum,designated as DMTp,has been ingeniously formulated.This new reagent can be produced with high efficiency through the simple combination of commercially available methyl 3-thiopropanoate and CD_(3)l.This novel SCD_(3) reagent exhibits excellent reactivity with electrophiles such as alkyl iodides,benzyl chlorides,aryl halides(l,Br)and aryl triflates,resulting in high levels of deuterium content(99%D).Representative deuterated methylthiolated biomolecules,such as Sulfoxaflor,havebeen synthesizedforuse in pharmaceutical discoveryand development.
基金supports were provided by National Key R&D Program of China (2021YFA1500200 and 2021YFF0701600)NSFC (22271249)the Fundamental Research Funds for the Central Universities (226-2022-00224 and 226-2023-00115).
文摘α-Olefins as aliphatic terminal alkenes could be obtained easily from numerous contemporary synthetic reactions as well as petro-chemical industry,and also found in natural products.Compared to the alkenes attaching the directing groups or activating group,the catalytic asymmetric reaction of unactivated terminal alkenes presents great challenges due to the weak electron effect and small steric hindrance effect.This review mainly summarizes the latest progress of the asymmetric reaction of unactivated terminal olefins since 2016.