The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the singl...The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given.The SET mechanism between ClO2and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200 88 kJ/mol.展开更多
Dearomative photocycloaddition of heteroarenes is an efficient method for replacing planar arenes with three-dimensional(3D)scaffolds,such as bicyclo[2.1.1]-hexane(BCH)containing heterocycles.Herein,we report intramol...Dearomative photocycloaddition of heteroarenes is an efficient method for replacing planar arenes with three-dimensional(3D)scaffolds,such as bicyclo[2.1.1]-hexane(BCH)containing heterocycles.Herein,we report intramolecular dearomative[2π+2σ]photocycloadditions of bicyclo[1.1.0]butanes(BCBs)with(benzo)furans and(benzo)thiophenes.These photocycloadditions are initiated through an energy transfer pathway(EnT)or single electron transfer pathway(SET),efficiently yielding unique BCHpyrrolidinone-fused heterocyclic scaffolds.Moreover,the synthetic utility of this photochemical reaction was demonstrated on the basis of large-scale synthesis and diversified transformations.Mechanistic investigations,in conjunction with density functional theory(DFT)calculations,were taken to support the proposed reaction mechanisms.展开更多
Treatment of ICF2CF2OCF2CF2SC2F (1) with organic halides in the presence of copper powder in a co-solvent DMF/HMPA( V/V= 1:1) gave the corresponding trifluoromethylated compounds in good to excellent yields. A copper ...Treatment of ICF2CF2OCF2CF2SC2F (1) with organic halides in the presence of copper powder in a co-solvent DMF/HMPA( V/V= 1:1) gave the corresponding trifluoromethylated compounds in good to excellent yields. A copper induced single electron transfer reaction mechanism is proposed.展开更多
The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.H...The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.展开更多
Alkyl chlorides are abundant and easily accessible starting materials.However,due to the high reduction potentials associated with unactivated alkyl chlorides,achieving their single electron reduction remains a persis...Alkyl chlorides are abundant and easily accessible starting materials.However,due to the high reduction potentials associated with unactivated alkyl chlorides,achieving their single electron reduction remains a persistent challenge.This challenge has spurred the exploration of efficient activation methods to overcome this issue.In recent years,photocatalysis has emerged as a mild and potent tool for the single electron reduction of unactivated alkyl chlorides,opening up new possibilities in this field.Considering the rapid advancements in this area,a comprehensive review that provides a conceptual understanding of this emerging field,with a specific focus on reaction design and catalytic mechanisms,would be timely and highly valuable.Hence,we present an overview of various synthetic techniques for photoinduced single electron reduction of unactivated alkyl chlorides.Furthermore,we also discuss the limitations of the present methods and future directions that lie ahead in this field.展开更多
Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of the...Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of them were isolated as stable crystals and studied by single-crystal X-ray diffraction,superconducting quantum interference device measurements,electron paramagnetic resonance,nuclear magnetic resonance,and UV–vis spectroscopy.Antiferromagnetic exchange coupling was observed among both 3 and 4.Radical anion and cation are basically separated in 3,while 4 featured a relatively strong anion-cationπ–πstacking interaction.This work demonstrated that the Lewis acid coupled electron transfer is an efficient way to prepare stable radical ion pairs.展开更多
A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. A plethora of methodologies were developed based on this concept, and transition metal-cat...A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. A plethora of methodologies were developed based on this concept, and transition metal-catalysis plays a central role among others catalysis systems own to its longstanding history. While a chemodivergent reaction based on organo-catalysis, especially photocatalysis, is rather limited as these concepts were only prevalent in the last two decades. With the ever-increasing importance of photocatalysis, a chemodivergent reaction based on such an activation pathway would be a meaningful direction. Herein, an efficient chemodivergent strategy for visible light photocatalysis is developed. By employing commercially available Rose Bengal as a photocatalyst, naturally occurring Viridicatin and its derivatives can be transformed into three different types of products through switchable single electron transfer (SET) or energy transfer (EnT) processes. Mechanistic studies have revealed that the oxygen as a reactive center, rather than carbon, is favored, which accounts for the first example of a C–O homo-dimerization product.展开更多
In this paper a projectile ion-recoil ion coincidence technique is used to investigate the transfer ionization processes in collisions of 0.22-6.30 MeV Cq＋ ions and 0.25-6.35 MeV 0q＋ ions （q=1, 2, 3, 4） with the H...In this paper a projectile ion-recoil ion coincidence technique is used to investigate the transfer ionization processes in collisions of 0.22-6.30 MeV Cq＋ ions and 0.25-6.35 MeV 0q＋ ions （q=1, 2, 3, 4） with the He atom separately. The cross section ratio f of transfer ionization to single electron transfer is measured, and the dependence of f on both charge state q and energy E of the projectiles is investigated. The electron-structure and the mechanisms leading to transfer ionization affect the dependence of f on q and E. Our measurements, along with other data published previously, suggest a similar dependence of f on charge state and energy of projectile for partially stripped ions over a large energy range. The maximum value of f is approximately 0.17q^0.60; the energy corresponding to maximum f is about 160q^0.60 keV/u.展开更多
Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the ...Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the half‐life of drug metabolism,enhance the efficacy of drugs,close metabolic sites,and decrease side effects.Thus,there is a rising demand for the practical construction of deuterium‐labeled drugs and their intermediates under mild conditions.This paper timely provides an overview of the recent advances in both photo‐and electro‐catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low‐cost and sustainable deuterium source.Three types of deuteration strategies are discussed according to the deuteration mode,named deuterium atom transfer strategy,deuterium atom abstraction strategy and deuterated water splitting strategy respectively.The application scope and mechanistic insights are discussed comprehensively.Finally,the perspective on the challenges and future development trends for photo‐and electro‐catalytic deuteration strategies are also presented.展开更多
Organosilicon compounds play an important role in the fields of materials science,pharmacy,and organic synthesis.The development of effective approaches for the preparation of these compounds have also become a resear...Organosilicon compounds play an important role in the fields of materials science,pharmacy,and organic synthesis.The development of effective approaches for the preparation of these compounds have also become a research focus in organic synthesis.In recent years,free radical synthesis of organosilicons has been vigorously developed,which generally has the advantages of milder synthesis conditions,higher yields and selectivity,and free of precious metal catalysts compared with traditional strategies.This article reviews research progresses in the synthesis of organosilico n compounds by free radical pathways since 2016.In most cases,the radical silylation is achieved based on the reaction of silyl radicals,which are triggered by four routes including peroxide,transition-metal-induced peroxide decomposition,alkali,photocatalysis.The alkyl radicals can also initiate the radical silylation for the generation of C(sp^(3))—Si bonds.展开更多
Spectroscopic investigations discovered that the in-situ generated phenylhydrazone anion was significantly bathochromically shifted to visible light region for photoactivation under irradiation. The photoexcited pheny...Spectroscopic investigations discovered that the in-situ generated phenylhydrazone anion was significantly bathochromically shifted to visible light region for photoactivation under irradiation. The photoexcited phenylhydrazone anion was potential to reduce aryl iodides via single electron transfer process for the subsequent radical chain reaction. A redox-neutral photochemical carbonylation of aryl iodides was developed on basis of the special spectroscopic features of phenylhydrazone anion. This protocol provided a convenient and efficient synthetic tool for accessing carbonylation products under redox neutral conditions without the need of transition-metals.展开更多
Herein, we report the first visible-light photoredox-catalyzed carboxylation of aryl epoxides with CO_(2)to synthesize hydroxy acid derivatives. A variety of valuable β-, γ-, δ-, ε–hydroxy acid derivatives are ob...Herein, we report the first visible-light photoredox-catalyzed carboxylation of aryl epoxides with CO_(2)to synthesize hydroxy acid derivatives. A variety of valuable β-, γ-, δ-, ε–hydroxy acid derivatives are obtained in moderate to high yields under mild conditions. This protocol shows noteworthy functionalgroup compatibility, high chemo-and regioselectivities under transition-metal-free conditions with an inexpensive organo-dye as photosensitizer. Mechanistic studies indicate that the benzylic carbanion is generated as an intermediate via the sequential single electron transfer(SSET) process.展开更多
On the basis of investigation of cyclic voltammetry, EPR spectroscopy and competition experiments, the nucleophilic substitution reaction of p- dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in...On the basis of investigation of cyclic voltammetry, EPR spectroscopy and competition experiments, the nucleophilic substitution reaction of p- dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in dimethyl sulfoxide giving ethyl α-cyano-α- (p-nitrophenyl) acetate is shown to take place via the intermediacy of p-dinitrobenzene radical anion. The reaction rate goes faster than that between p-nitrohalobenzenes and the same sodium salt of ethyl α-cyanoacetate carbanion. There is an evidence for a single electron transfer mechanism.展开更多
The demand and pursuit of chemical entities with UV filtration and antioxidant properties for enhanced photoprotection have been driven in recent times by acute exposure of humans to solar ultraviolet radiations. The ...The demand and pursuit of chemical entities with UV filtration and antioxidant properties for enhanced photoprotection have been driven in recent times by acute exposure of humans to solar ultraviolet radiations. The structural, electronic, antioxidant and UV absorption properties of drometrizole (PBT) and designed ortho-substituted derivatives are reported via DFT and TD-DFT in the gas and aqueous phases. DFT and TD-DFT computations were performed at the M062x-D3Zero/6-311++G(d,p)//B97-3c and PBE0-D3(BJ)/def2-TZVP levels of theory respectively. Reaction enthalpies related to hydrogen atom transfer (HAT), single-electron transfer followed by proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET) mechanisms were computed and compared with those of phenol. Results show that the presence of -NH2 substituent reduces the O-H bond dissociation enthalpy and ionization potential, while that of -CN increases the proton affinity. The HAT and SPLET mechanisms are the most plausible in the gas and aqueous phases respectively. The molecule with the -NH2 substituent (PBT1) was identified to be the compound with the highest antioxidant activity. The UV spectra of the studied compounds are characterized by two bands in the 280 - 400 nm regions. Results from this study provide a better comprehension antioxidant mechanism of drometrizole and present a new perspective for the design of electron-donor antioxidant molecules with enhanced antioxidant-photoprotective efficiencies for applications in commercial sunscreens.展开更多
The catalytic difunctionalization of alkenes offers an efficient and straightforward approach to incorporating two functional groups across a double bond for increasing molecular complexity and has found widespread ap...The catalytic difunctionalization of alkenes offers an efficient and straightforward approach to incorporating two functional groups across a double bond for increasing molecular complexity and has found widespread application in organic synthesis.Among them,photo-/electrocatalytic difunctionalization of alkenes based on the radical-polar crossover strategy has gained increasing attention.This approach not only aligns with the principles of green and sustainable chemistry but also uniquely merges both radical and ionic modes of reactivity,overcoming the inherent limitations of conventional methodologies.This review summarizes the innovative progress in photo-/electrocatalytic difunctionalization of alkenes over the last decade,which is focused on the transformations via oxidative radical-polar crossover(ORPC)or reductive radical-polar crossover(RRPC)as the key step and particular emphasizes on the selection of functionalized polar adducts.展开更多
Catalyst innovation lies at the heart of transition-metal-catalyzed reaction development.In this article,we have explored the C(sp2)–H alkenylation activity with novel spirocyclic N-heterocyclic carbene(NHC)-based cy...Catalyst innovation lies at the heart of transition-metal-catalyzed reaction development.In this article,we have explored the C(sp2)–H alkenylation activity with novel spirocyclic N-heterocyclic carbene(NHC)-based cyclometalated ruthenium pincer catalyst system,SNRu-X.After screening catalyst and condition,a high valent Ru(Ⅳ)dioxide(X=O_(2))species has demonstrated superior reactivity in the catalytic alkenylation of aromatic and olefinic C–H bonds with unactivated alkenyl bromides and triflates.This reaction has achieved the easy construction of a wide range of(hetero)aromatic alkenes and dienes,in good to excellent yields with exclusive selectivity.Preliminary mechanistic studies indicate that this reaction may proceed through a single electron transfer(SET)triggered oxidative addition,by doing so,providing valuable complementary to classical alkenylation reactions that are dependent on activated alkenyl precursors.展开更多
Comprehensive Summary The conversion of CF3-alkenes to gem-difluoroalkenes using reductive cross-coupling strategy has received much attention in recent years,however,the use of green and readily available reducing sa...Comprehensive Summary The conversion of CF3-alkenes to gem-difluoroalkenes using reductive cross-coupling strategy has received much attention in recent years,however,the use of green and readily available reducing salt to mediate these reactions remains to be explored.In this work,a concise construction of gem-difluoroalkenes,which requires neither a catalyst nor a metal reducing agent,was established.Rongalite,a safe and inexpensive industrial product,was employed as both a radical initiator and reductant.This procedure was compatible with both linear and cyclic diaryliodonium salts,enabling a wide variety of substrates(>70 examples).The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.展开更多
文摘The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given.The SET mechanism between ClO2and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200 88 kJ/mol.
基金supported by the National Key R&D Program of China(2022YFC2303100)the National Natural Science Foundation of China(22305261,21372250,21121062,21302203,20732008,21772037,21772226,21861132014,91956115,22171078)+1 种基金the Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)the Fundamental Research Funds for the Central Universities(222201717003)。
文摘Dearomative photocycloaddition of heteroarenes is an efficient method for replacing planar arenes with three-dimensional(3D)scaffolds,such as bicyclo[2.1.1]-hexane(BCH)containing heterocycles.Herein,we report intramolecular dearomative[2π+2σ]photocycloadditions of bicyclo[1.1.0]butanes(BCBs)with(benzo)furans and(benzo)thiophenes.These photocycloadditions are initiated through an energy transfer pathway(EnT)or single electron transfer pathway(SET),efficiently yielding unique BCHpyrrolidinone-fused heterocyclic scaffolds.Moreover,the synthetic utility of this photochemical reaction was demonstrated on the basis of large-scale synthesis and diversified transformations.Mechanistic investigations,in conjunction with density functional theory(DFT)calculations,were taken to support the proposed reaction mechanisms.
基金Project supported by the National Natural Science Foundation of China.
文摘Treatment of ICF2CF2OCF2CF2SC2F (1) with organic halides in the presence of copper powder in a co-solvent DMF/HMPA( V/V= 1:1) gave the corresponding trifluoromethylated compounds in good to excellent yields. A copper induced single electron transfer reaction mechanism is proposed.
基金financially supported by the National Natural Science Foundation of China(Nos.92061110,21925303,21829501,21771186,21222301,21528303,and 21171170)the Anhui Provincial Natural Science Foundation(2108085Y05 and 2108085MB56)+1 种基金Collaborative Innovation Program of Hefei Science Center,CAS(Nos.2020HSCCIP005 and 2022HSC-CIP018)the Hefei National Laboratory for Physical Sciences at the Microscale(KF2020102).
文摘The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.
基金supported by the National Natural Science Foundation of China (22001248)the Fundamental Research Funds for the Central Universitiesthe University of the Chinese Academy of Sciences。
文摘Alkyl chlorides are abundant and easily accessible starting materials.However,due to the high reduction potentials associated with unactivated alkyl chlorides,achieving their single electron reduction remains a persistent challenge.This challenge has spurred the exploration of efficient activation methods to overcome this issue.In recent years,photocatalysis has emerged as a mild and potent tool for the single electron reduction of unactivated alkyl chlorides,opening up new possibilities in this field.Considering the rapid advancements in this area,a comprehensive review that provides a conceptual understanding of this emerging field,with a specific focus on reaction design and catalytic mechanisms,would be timely and highly valuable.Hence,we present an overview of various synthetic techniques for photoinduced single electron reduction of unactivated alkyl chlorides.Furthermore,we also discuss the limitations of the present methods and future directions that lie ahead in this field.
基金the National Key R&D Program of China(grant no.2018YFA0306004)the National Natural Science Foundation of China(grant no.21525102)for their financial support.
文摘Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of them were isolated as stable crystals and studied by single-crystal X-ray diffraction,superconducting quantum interference device measurements,electron paramagnetic resonance,nuclear magnetic resonance,and UV–vis spectroscopy.Antiferromagnetic exchange coupling was observed among both 3 and 4.Radical anion and cation are basically separated in 3,while 4 featured a relatively strong anion-cationπ–πstacking interaction.This work demonstrated that the Lewis acid coupled electron transfer is an efficient way to prepare stable radical ion pairs.
基金the National Natural Science Foundation of China(No.22061012)the Excellent Young Talents Plan of Guizhou Medical University(No.[2023]105)+1 种基金the GMU Training Program of the National Natural Science Foundation of China(No.22NSFCP13)the support from National-Local Joint Engineering Research Center for Innovative&Generic Chemical Drug&Guizhou Province Innovation Base of Common Major Chronic Disease Pathogenesis and Drug Development and Application(No.[2021]4029).
文摘A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. A plethora of methodologies were developed based on this concept, and transition metal-catalysis plays a central role among others catalysis systems own to its longstanding history. While a chemodivergent reaction based on organo-catalysis, especially photocatalysis, is rather limited as these concepts were only prevalent in the last two decades. With the ever-increasing importance of photocatalysis, a chemodivergent reaction based on such an activation pathway would be a meaningful direction. Herein, an efficient chemodivergent strategy for visible light photocatalysis is developed. By employing commercially available Rose Bengal as a photocatalyst, naturally occurring Viridicatin and its derivatives can be transformed into three different types of products through switchable single electron transfer (SET) or energy transfer (EnT) processes. Mechanistic studies have revealed that the oxygen as a reactive center, rather than carbon, is favored, which accounts for the first example of a C–O homo-dimerization product.
文摘In this paper a projectile ion-recoil ion coincidence technique is used to investigate the transfer ionization processes in collisions of 0.22-6.30 MeV Cq＋ ions and 0.25-6.35 MeV 0q＋ ions （q=1, 2, 3, 4） with the He atom separately. The cross section ratio f of transfer ionization to single electron transfer is measured, and the dependence of f on both charge state q and energy E of the projectiles is investigated. The electron-structure and the mechanisms leading to transfer ionization affect the dependence of f on q and E. Our measurements, along with other data published previously, suggest a similar dependence of f on charge state and energy of projectile for partially stripped ions over a large energy range. The maximum value of f is approximately 0.17q^0.60; the energy corresponding to maximum f is about 160q^0.60 keV/u.
文摘Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the half‐life of drug metabolism,enhance the efficacy of drugs,close metabolic sites,and decrease side effects.Thus,there is a rising demand for the practical construction of deuterium‐labeled drugs and their intermediates under mild conditions.This paper timely provides an overview of the recent advances in both photo‐and electro‐catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low‐cost and sustainable deuterium source.Three types of deuteration strategies are discussed according to the deuteration mode,named deuterium atom transfer strategy,deuterium atom abstraction strategy and deuterated water splitting strategy respectively.The application scope and mechanistic insights are discussed comprehensively.Finally,the perspective on the challenges and future development trends for photo‐and electro‐catalytic deuteration strategies are also presented.
基金the Fundamental Research Funds for the Central Universities(No.30920021120)Key Laboratory of Biomass Energy and Material,Jiangsu Province(No.JSBEM201912)+1 种基金the National Natural Science Foundation of China(No.21905089)the Chinese Postdoctoral Science Foundation(No.2019M662775)for financial support。
文摘Organosilicon compounds play an important role in the fields of materials science,pharmacy,and organic synthesis.The development of effective approaches for the preparation of these compounds have also become a research focus in organic synthesis.In recent years,free radical synthesis of organosilicons has been vigorously developed,which generally has the advantages of milder synthesis conditions,higher yields and selectivity,and free of precious metal catalysts compared with traditional strategies.This article reviews research progresses in the synthesis of organosilico n compounds by free radical pathways since 2016.In most cases,the radical silylation is achieved based on the reaction of silyl radicals,which are triggered by four routes including peroxide,transition-metal-induced peroxide decomposition,alkali,photocatalysis.The alkyl radicals can also initiate the radical silylation for the generation of C(sp^(3))—Si bonds.
基金supported by the National Natural Science Foundation of China (Nos.22271246 and 22101251)Yunling Scholar Project of "Yunnan Revitalization Talent Support Program" for financial support。
文摘Spectroscopic investigations discovered that the in-situ generated phenylhydrazone anion was significantly bathochromically shifted to visible light region for photoactivation under irradiation. The photoexcited phenylhydrazone anion was potential to reduce aryl iodides via single electron transfer process for the subsequent radical chain reaction. A redox-neutral photochemical carbonylation of aryl iodides was developed on basis of the special spectroscopic features of phenylhydrazone anion. This protocol provided a convenient and efficient synthetic tool for accessing carbonylation products under redox neutral conditions without the need of transition-metals.
基金the National Natural Science Foundation of China (Nos. 22225106, 22301193)Fundamental Research Funds from Sichuan University (No. 2020SCUNL102)the Fundamental Research Funds for the Central Universities。
文摘Herein, we report the first visible-light photoredox-catalyzed carboxylation of aryl epoxides with CO_(2)to synthesize hydroxy acid derivatives. A variety of valuable β-, γ-, δ-, ε–hydroxy acid derivatives are obtained in moderate to high yields under mild conditions. This protocol shows noteworthy functionalgroup compatibility, high chemo-and regioselectivities under transition-metal-free conditions with an inexpensive organo-dye as photosensitizer. Mechanistic studies indicate that the benzylic carbanion is generated as an intermediate via the sequential single electron transfer(SSET) process.
文摘On the basis of investigation of cyclic voltammetry, EPR spectroscopy and competition experiments, the nucleophilic substitution reaction of p- dinitrobenzene with the sodium salt of ethyl α-cyanoacetate carbanion in dimethyl sulfoxide giving ethyl α-cyano-α- (p-nitrophenyl) acetate is shown to take place via the intermediacy of p-dinitrobenzene radical anion. The reaction rate goes faster than that between p-nitrohalobenzenes and the same sodium salt of ethyl α-cyanoacetate carbanion. There is an evidence for a single electron transfer mechanism.
文摘The demand and pursuit of chemical entities with UV filtration and antioxidant properties for enhanced photoprotection have been driven in recent times by acute exposure of humans to solar ultraviolet radiations. The structural, electronic, antioxidant and UV absorption properties of drometrizole (PBT) and designed ortho-substituted derivatives are reported via DFT and TD-DFT in the gas and aqueous phases. DFT and TD-DFT computations were performed at the M062x-D3Zero/6-311++G(d,p)//B97-3c and PBE0-D3(BJ)/def2-TZVP levels of theory respectively. Reaction enthalpies related to hydrogen atom transfer (HAT), single-electron transfer followed by proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET) mechanisms were computed and compared with those of phenol. Results show that the presence of -NH2 substituent reduces the O-H bond dissociation enthalpy and ionization potential, while that of -CN increases the proton affinity. The HAT and SPLET mechanisms are the most plausible in the gas and aqueous phases respectively. The molecule with the -NH2 substituent (PBT1) was identified to be the compound with the highest antioxidant activity. The UV spectra of the studied compounds are characterized by two bands in the 280 - 400 nm regions. Results from this study provide a better comprehension antioxidant mechanism of drometrizole and present a new perspective for the design of electron-donor antioxidant molecules with enhanced antioxidant-photoprotective efficiencies for applications in commercial sunscreens.
基金the National Natural Science Foundation of China(Nos.22001108 and 22271245)JiangxiProvince Science and Technology Project(No.20243BCE51084 and 20242BAB25126)+1 种基金Taishan Scholars Construction Projects of Shandong(tsqn202408199)the Open Research Fund of School of Chemistry and Chemical Engineering,and Henan Normal University(No.2021zD01)for financial support.
文摘The catalytic difunctionalization of alkenes offers an efficient and straightforward approach to incorporating two functional groups across a double bond for increasing molecular complexity and has found widespread application in organic synthesis.Among them,photo-/electrocatalytic difunctionalization of alkenes based on the radical-polar crossover strategy has gained increasing attention.This approach not only aligns with the principles of green and sustainable chemistry but also uniquely merges both radical and ionic modes of reactivity,overcoming the inherent limitations of conventional methodologies.This review summarizes the innovative progress in photo-/electrocatalytic difunctionalization of alkenes over the last decade,which is focused on the transformations via oxidative radical-polar crossover(ORPC)or reductive radical-polar crossover(RRPC)as the key step and particular emphasizes on the selection of functionalized polar adducts.
基金suported by the National Natural Science Foundation of China(2187,1117,91956203)the“111”Program of Minister of Education,Beijing National Laboratory for Molecular Sciences(BNLMS202109)the Science and Technology Commission of Shanghai Municipality(19JC1430100)。
文摘Catalyst innovation lies at the heart of transition-metal-catalyzed reaction development.In this article,we have explored the C(sp2)–H alkenylation activity with novel spirocyclic N-heterocyclic carbene(NHC)-based cyclometalated ruthenium pincer catalyst system,SNRu-X.After screening catalyst and condition,a high valent Ru(Ⅳ)dioxide(X=O_(2))species has demonstrated superior reactivity in the catalytic alkenylation of aromatic and olefinic C–H bonds with unactivated alkenyl bromides and triflates.This reaction has achieved the easy construction of a wide range of(hetero)aromatic alkenes and dienes,in good to excellent yields with exclusive selectivity.Preliminary mechanistic studies indicate that this reaction may proceed through a single electron transfer(SET)triggered oxidative addition,by doing so,providing valuable complementary to classical alkenylation reactions that are dependent on activated alkenyl precursors.
基金supported by the National Natural Science Foundation of China(Grants 21971080,21971079,21772051)This work was also supported by the 111 Project B17019.
文摘Comprehensive Summary The conversion of CF3-alkenes to gem-difluoroalkenes using reductive cross-coupling strategy has received much attention in recent years,however,the use of green and readily available reducing salt to mediate these reactions remains to be explored.In this work,a concise construction of gem-difluoroalkenes,which requires neither a catalyst nor a metal reducing agent,was established.Rongalite,a safe and inexpensive industrial product,was employed as both a radical initiator and reductant.This procedure was compatible with both linear and cyclic diaryliodonium salts,enabling a wide variety of substrates(>70 examples).The utility of this approach was demonstrated through gram-scale synthesis and efficient late-stage functionalizations of anti-inflammatory drugs.
