Herein,we report an iron-promoted carbonylation-rearrangement ofα-aminoaryl-tethered alkylidene cyclopropanes with CO_(2)to generate quinolinofuran derivatives.A variety of quinolinofuran derivatives are obtained in ...Herein,we report an iron-promoted carbonylation-rearrangement ofα-aminoaryl-tethered alkylidene cyclopropanes with CO_(2)to generate quinolinofuran derivatives.A variety of quinolinofuran derivatives are obtained in moderate to excellent yields,and two promising luminescent material molecules have been synthesized using the developed method.The Lewis acid Fe Cl_(3)was introduced into this reaction,which effectively promoted the ring opening and rearrangement of cyclopropanes.This reaction features a broad substrate scope,satisfactory functional group tolerance,facile scalability,and easy derivatization of the products.展开更多
Herein, a facile synthesis of valuable pyrido[1,2-a]pyrimidine-4-thiones is reported via novel thiocarbonylation of C(sp^(3))-H bonds with carbon disulfide(CS_(2)). This reaction features easy availability of substrat...Herein, a facile synthesis of valuable pyrido[1,2-a]pyrimidine-4-thiones is reported via novel thiocarbonylation of C(sp^(3))-H bonds with carbon disulfide(CS_(2)). This reaction features easy availability of substrates,good functional group tolerance, high yields, facile scalability and atom economy. Mechanistic investigations indicate that sulfate anion and sulfuric anhydride anion might be involved in this reaction.展开更多
With the increasing awareness of sustainable chemistry and green chemistry,catalytic conversion of carbon dioxide(CO_(2))into high value‐added and bulk chemicals is a promising tech‐nology that can utilize CO_(2) as...With the increasing awareness of sustainable chemistry and green chemistry,catalytic conversion of carbon dioxide(CO_(2))into high value‐added and bulk chemicals is a promising tech‐nology that can utilize CO_(2) as an ideal C1 source while simulta‐neously storing renewable energy.Despite being frustrated with its thermodynamic stability and kinetic inertness,CO_(2) has been tamed for triggering catalytic constructions of highly‐valued entities like important hydrocarbon fuels and fine chemicals,mainly aiding by two scenarios:CO_(2) reduction and CO_(2)‐involved organic synthesis.Accordingly,science,industry and govern‐ment agencies have been devoted to leverage these synthetic tools in targeting the catalytic conversion of CO_(2).Therefore,it motivates us to organize the special column of“Catalytic Con‐version of CO_(2)”.The column contains 14 papers,including 4 reviews,4 communications and 6 articles,which cover the frontiers and most of the research aspects of catalytic con‐version of CO_(2).展开更多
Dicarboxylic acids have a wide range of applications in the polymer industry to construct valuable materials.Photocatalysis has recently emerged as an efficient and sustainable strategy to generate dicarboxylic acids....Dicarboxylic acids have a wide range of applications in the polymer industry to construct valuable materials.Photocatalysis has recently emerged as an efficient and sustainable strategy to generate dicarboxylic acids.However,photocatalytic dicarboxylation with CO_(2) is mainly limited to unsaturated bonds,and the dicarboxylation of C-C single bonds still remains a challenge.Herein,we report a photocatalytic dicarboxylation of C-C single bonds in strained rings with CO_(2) units via consecutive photo-induced electron transfer(ConPET).It is also the first photocatalytic reductive ring-opening reaction of cyclobutanes.Notably,this transition-metal-free protocol exhibits good functional group tolerance,broad substrate scope,facile scalability,and easy product derivatizations.Moreover,diacids can easily be derivatized to mainchain liquid crystalline polyesters.展开更多
The carboxylation of readily available organo halides with CO_(2)represents a practical strategy to afford valuable carboxylic acids.However,efficient carboxylation of inexpensive unactivated alkyl chlorides is still ...The carboxylation of readily available organo halides with CO_(2)represents a practical strategy to afford valuable carboxylic acids.However,efficient carboxylation of inexpensive unactivated alkyl chlorides is still underdeveloped.Herein,we report the electro-reductive carboxylation of C–Cl bonds in unactivated chlorides and polyvinyl chloride with CO_(2).A variety of alkyl carboxylic acids are obtained in moderate to good yields under mild conditions with high chemoselectivity.Importantly,the utility of this electroreductive carboxylation is demonstrated with great potential in polyvinyl chloride(PVC)upgrading,which could convert discarded PVC from hydrophobic to hydrophilic functional products.Mechanistic experiments support the successive single electron reduction of unactivated chlorides to generate alkyl anion species and following nucleophilic attack on CO_(2)to give desired products.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
Chiral compounds play a crucial role in the development of pharmaceuticals,pesticides,fragrances,and materials due to their unique stereochemical configurations.Asymmetric catalysis,which employs chiral catalysts to f...Chiral compounds play a crucial role in the development of pharmaceuticals,pesticides,fragrances,and materials due to their unique stereochemical configurations.Asymmetric catalysis,which employs chiral catalysts to favor the production of one enantiomer over its mirror image,has emerged as a pivotal technique in the synthesis of chiral compounds[1].However,traditional asymmetric methods sometimes rely on environmentally harmful reducing or oxidizing agents,presenting a considerable challenge in the pursuit of green chemistry.展开更多
The direct C(sp^(3))-H functionalization of abundant hydrocarbons for enantioselective synthesis of high-value chiral compounds has attracted significant attention from both academia and industry. This method is highl...The direct C(sp^(3))-H functionalization of abundant hydrocarbons for enantioselective synthesis of high-value chiral compounds has attracted significant attention from both academia and industry. This method is highly regarded for its inherent atom and step economy as well as abundant starting materials [1].展开更多
Herein,we present a visible-light-driven carbo-carboxylation of alkenes with CO_(2) via catalytic electron donor-acceptor(EDA)complex activation.A variety of oxindole-3-acetic acid and derivatives were generated in mo...Herein,we present a visible-light-driven carbo-carboxylation of alkenes with CO_(2) via catalytic electron donor-acceptor(EDA)complex activation.A variety of oxindole-3-acetic acid and derivatives were generated in moderate to excellent yields from N-arylacrylamides and CO_(2).Mechanistic studies revealed the formation of an EDA complex between catalytic thiolate and alkene.Notably,this redox-neutral reaction features mild,transition-metal and photocatalyst-free conditions,good functional group tolerance and broad substrate scope.Furthermore,the facile synthesis of key intermediates in natural products underscores the utility of this methodology.展开更多
Isofunctional reactions involving the cleavage of carbon-carbon double bonds(C=C)hold an important position in organic synthesis,as they allow for the restructuring of alkene carbon chains and enable the exchange of f...Isofunctional reactions involving the cleavage of carbon-carbon double bonds(C=C)hold an important position in organic synthesis,as they allow for the restructuring of alkene carbon chains and enable the exchange of functional groups without introducing exogenous groups.Currently,these reactions are primarily divided into C=C/C=C metathesis and C=C/C=O metathesis,with most relying on the use of transition metal catalysts.We report herein a C=C/CH_(2) metathesis reaction that obviates the need for transition metals and directing groups,and is characterized by economic and straightforward operation.This reaction not only facilitates the replacement of nitriles with ketones,but also enables the replacement of ketones with nitriles,demonstrating great universality.展开更多
In recent years, visible light-driven organic photochemical synthesis has attracted wide research interest from academic and industrial communities due to its features of green and sustainable chemistry. In this flour...In recent years, visible light-driven organic photochemical synthesis has attracted wide research interest from academic and industrial communities due to its features of green and sustainable chemistry. In this flourishing area, Chinese chemists have devoted great efforts to different aspects of synthetic chemistry. This review will summarize their representative work according to the following categories: C–H functionalization, synthesis of aromatic aza-heterocycles, asymmetric organic photochemical synthesis, transformations of small molecules and biomolecule-compatible reactions.展开更多
Carbon dioxide(CO2)is an important and appealing C1 building block in chemical synthesis due to its nontoxicity,abundance,availability and sustainability.Tremendous progress has been achieved in the chemical transform...Carbon dioxide(CO2)is an important and appealing C1 building block in chemical synthesis due to its nontoxicity,abundance,availability and sustainability.Tremendous progress has been achieved in the chemical transformation of CO2 into high valueadded organic chemicals.However,the asymmetric synthesis with CO2 to form enantioenriched molecules,especially the catalytic process,has lagged far behind.The enantioselective incorporation of CO2 into organic compounds is highly desirable,as the corresponding chiral products,such as carboxylic acids and amino acids,are common structural units in a vast array of natural products and biologically active compounds.Herein,we discuss recent progress toward the enantioselective incorporation of CO2 into organic molecules,which mainly rely on three strategies:1)kinetic resolution or desymmetrization of epoxides with CO2 to form chiral cyclic carbonates and polycarbonates;2)nucleophilic attack of O-or N-nucleophiles to CO2 in tandem with asymmetric C–O bond formation to prepare chiral cyclic carbonates and carbamates;3)direct enantioselective nucleophilic attack of organometallic reagents to CO2 with asymmetric C–C bond formation.Finally,challenges and future outlook in this area are also presented.展开更多
Herein we report a novel visible-light-mediated external reductant-free reductive cross coupling for the construction of C sp2–C sp3 bonds.A variety of benzylammonium salts underwent selective coupling with(hetero)ar...Herein we report a novel visible-light-mediated external reductant-free reductive cross coupling for the construction of C sp2–C sp3 bonds.A variety of benzylammonium salts underwent selective coupling with(hetero)aryl nitriles to deliver important diarylmethanes under mild reaction conditions.Importantly,photocatalysts can be omitted for many cases,which might involve the electron donor acceptor(EDA)complex.Mechanistic studies indicated benzylic radicals might be involved as the key intermediates.Moreover,the in situ generated NMe3 via cleavage of C–N bond in ammonium salts acts as the electron donor,thus avoiding the use of external-reductant.展开更多
Herein, we report a novel synthesis of 1,3-oxazin-6-ones from enamides with CO2 through C--H carboxylation and one-pot cyclization. This transition-metal-free and redox-neutral process features broad substrate scope, ...Herein, we report a novel synthesis of 1,3-oxazin-6-ones from enamides with CO2 through C--H carboxylation and one-pot cyclization. This transition-metal-free and redox-neutral process features broad substrate scope, good functional group tolerance and facile product derivatization. The nucleophilic attack to CO2 from the electron-rich alkene is demonstrated for this reaction.展开更多
Prediction of reaction yields using machine learning(ML)can help chemists select high-yielding reactions and provide prior experience before wet-lab experimenting to improve efficiency.However,the exploration of a mul...Prediction of reaction yields using machine learning(ML)can help chemists select high-yielding reactions and provide prior experience before wet-lab experimenting to improve efficiency.However,the exploration of a multicomponent organic reaction features many complex variables and limited number of experimental data,which are challenging for the application of ML.Herein,we perform yield prediction for the synthesis of 2-oxazolidones via Cu-catalyzed radical-type oxy-alkylation of allylamines and herteroaryl-methylamines with CO_(2),which is a three-component reaction.Using physicochemical descriptors as features to launch ML modelling,we find that XGBoost shows significantly improved performance over linear models and these features are effective for the yield prediction.Moreover,out-of-sample prediction indicates the application potential of the model.This study demonstrates great potential of regression-modelling-based ML in organic synthesis even with complex factors and a general small size of reaction data,which are generated from the classical research pattern of method for the inquiry of multicomponent reactions.展开更多
Summary of main observation and conclusion A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C-O activation of enolates was developed.Besides ketones,aldeh...Summary of main observation and conclusion A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C-O activation of enolates was developed.Besides ketones,aldehydes were also suitable substrates for the presented catalytic system to produce di-or tri-substituted olefins.It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols,which could not survive in other reported routes for converting carbonyl compounds to olefins.This method also showed good regio-and stereo-selectivity for olefin products.Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C-O activation of enolates,thus offering helpful contribution to current enol chemistry.展开更多
Summary of main observation and conclusion The radical-initiated carboxylativecyclization of allylamines with CO_(2)represents an efficientand highly promising strategy to afford valuable 2-oxazolidinones.However,the ...Summary of main observation and conclusion The radical-initiated carboxylativecyclization of allylamines with CO_(2)represents an efficientand highly promising strategy to afford valuable 2-oxazolidinones.However,the radical precursorsand pathways to generate radicals in such processes are still lim-ited.Herein,we report the firstCu-catalyzed selective oxy-cyanoalkylation of allylamines with cycloketone oxime esters and CO_(2)viaC-C bond cleavage.Many cyanoalkyl-substituted 2-oxazolidinones are obtained in moderate togood yields withhigh regio-and chemo-selectivities.The utility ofthis re-dox-neutral and cyanide-free method is demonstrated with mild conditions,broad substrate scope,good functional group tolerance and easy scalability.展开更多
Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2...Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.展开更多
Herein,we report a novel protocol for visible-light-driven alkylative carboxylation of alkenes with CO_(2) in the absence of external photocatalyst.Under the irradiation of visible light,a variety of 4-alkyl-1,4-dihyd...Herein,we report a novel protocol for visible-light-driven alkylative carboxylation of alkenes with CO_(2) in the absence of external photocatalyst.Under the irradiation of visible light,a variety of 4-alkyl-1,4-dihydropyridines(alkyl-DHPs)serve as not only alkyl radical precursors but also photoexcited reductants probably with the potential to reduce benzyl radicals.Several styrenes and acrylates are applicable in this reaction to give structurally diverse carboxylic acids in good to excellent yields.These reactions feature mild reaction conditions(1 atm of CO_(2),room temperature,visible light,photocatalyst-and transition metalfree),good functional group tolerance,easy scalability,as well as high regio-,and chemo-selectivity.Mechanistic investigations provide evidence that alkyl radical,benzyl radical and carbanion might be involved in this reaction,providing a novel strategy for CO_(2) utilization.展开更多
Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In ...Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In contrast to the well-developed functionalization of one carbon fragment after C–C bond cleavage,herein,we report a novel electro-reductive carboxylation of C(sp^(3))–C(sp^(3))bond in multi-aryl ethanes with carbon dioxide(CO_(2))by utilizing both carbon fragments.Thus,this reaction exhibits an atom-,step-economic approach for the synthesis of carboxylic acids,fulfilling principal aspirations of organic synthesis.Moreover,this method features mild reaction conditions,broad substrate scope,and good functional group tolerance.Symmetric and asymmetric substrates bearing primary,secondary,or tertiary C(sp^(3))–C(sp^(3))bonds are all amenable to this strategy,enabling one or two structurally different carboxylic acids to be facilely constructed at the same time.Mechanistic investigations indicate that carbanions might be the key intermediates in this reaction,which could be captured by CO_(2)efficiently.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.21801025,22225106)Natural Science Foundation of Sichuan Province(No.2022NSFSC0200)Sichuan Science and Technology Program(No.MZGC20230100)。
文摘Herein,we report an iron-promoted carbonylation-rearrangement ofα-aminoaryl-tethered alkylidene cyclopropanes with CO_(2)to generate quinolinofuran derivatives.A variety of quinolinofuran derivatives are obtained in moderate to excellent yields,and two promising luminescent material molecules have been synthesized using the developed method.The Lewis acid Fe Cl_(3)was introduced into this reaction,which effectively promoted the ring opening and rearrangement of cyclopropanes.This reaction features a broad substrate scope,satisfactory functional group tolerance,facile scalability,and easy derivatization of the products.
基金the National Natural Science Foundation of China (No. 21822108)Sichuan Science and Technology Program (Nos.20CXTD0112, 2020YJ0491)+1 种基金National Key Research and Development Program of China (No. 2018YFC1602101)the Fundamental Research Funds for the Central Universities。
文摘Herein, a facile synthesis of valuable pyrido[1,2-a]pyrimidine-4-thiones is reported via novel thiocarbonylation of C(sp^(3))-H bonds with carbon disulfide(CS_(2)). This reaction features easy availability of substrates,good functional group tolerance, high yields, facile scalability and atom economy. Mechanistic investigations indicate that sulfate anion and sulfuric anhydride anion might be involved in this reaction.
文摘With the increasing awareness of sustainable chemistry and green chemistry,catalytic conversion of carbon dioxide(CO_(2))into high value‐added and bulk chemicals is a promising tech‐nology that can utilize CO_(2) as an ideal C1 source while simulta‐neously storing renewable energy.Despite being frustrated with its thermodynamic stability and kinetic inertness,CO_(2) has been tamed for triggering catalytic constructions of highly‐valued entities like important hydrocarbon fuels and fine chemicals,mainly aiding by two scenarios:CO_(2) reduction and CO_(2)‐involved organic synthesis.Accordingly,science,industry and govern‐ment agencies have been devoted to leverage these synthetic tools in targeting the catalytic conversion of CO_(2).Therefore,it motivates us to organize the special column of“Catalytic Con‐version of CO_(2)”.The column contains 14 papers,including 4 reviews,4 communications and 6 articles,which cover the frontiers and most of the research aspects of catalytic con‐version of CO_(2).
基金Financial support is provided by the National Natural Science Foundation of China(No.22225106)Fundamental Research Funds from Sichuan University(No.2020SCUNL102)the Fundamental Research Funds for the Central Universities。
文摘Dicarboxylic acids have a wide range of applications in the polymer industry to construct valuable materials.Photocatalysis has recently emerged as an efficient and sustainable strategy to generate dicarboxylic acids.However,photocatalytic dicarboxylation with CO_(2) is mainly limited to unsaturated bonds,and the dicarboxylation of C-C single bonds still remains a challenge.Herein,we report a photocatalytic dicarboxylation of C-C single bonds in strained rings with CO_(2) units via consecutive photo-induced electron transfer(ConPET).It is also the first photocatalytic reductive ring-opening reaction of cyclobutanes.Notably,this transition-metal-free protocol exhibits good functional group tolerance,broad substrate scope,facile scalability,and easy product derivatizations.Moreover,diacids can easily be derivatized to mainchain liquid crystalline polyesters.
基金provided by the National Natural Science Foundation of China(Nos.22225106,22201027)Fundamental Research Funds for the Central Universities。
文摘The carboxylation of readily available organo halides with CO_(2)represents a practical strategy to afford valuable carboxylic acids.However,efficient carboxylation of inexpensive unactivated alkyl chlorides is still underdeveloped.Herein,we report the electro-reductive carboxylation of C–Cl bonds in unactivated chlorides and polyvinyl chloride with CO_(2).A variety of alkyl carboxylic acids are obtained in moderate to good yields under mild conditions with high chemoselectivity.Importantly,the utility of this electroreductive carboxylation is demonstrated with great potential in polyvinyl chloride(PVC)upgrading,which could convert discarded PVC from hydrophobic to hydrophilic functional products.Mechanistic experiments support the successive single electron reduction of unactivated chlorides to generate alkyl anion species and following nucleophilic attack on CO_(2)to give desired products.
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Chiral compounds play a crucial role in the development of pharmaceuticals,pesticides,fragrances,and materials due to their unique stereochemical configurations.Asymmetric catalysis,which employs chiral catalysts to favor the production of one enantiomer over its mirror image,has emerged as a pivotal technique in the synthesis of chiral compounds[1].However,traditional asymmetric methods sometimes rely on environmentally harmful reducing or oxidizing agents,presenting a considerable challenge in the pursuit of green chemistry.
文摘The direct C(sp^(3))-H functionalization of abundant hydrocarbons for enantioselective synthesis of high-value chiral compounds has attracted significant attention from both academia and industry. This method is highly regarded for its inherent atom and step economy as well as abundant starting materials [1].
基金support is provided by the National Key R&D Program of China(2024YFA1509702)the National Natural Science Foundation of China(22225106,22101191)+1 种基金the Sichuan Science and Technology Program(2024ZYD0101)the Fundamental Research Funds for the Central Universities and the Open Research Fund of State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University.
文摘Herein,we present a visible-light-driven carbo-carboxylation of alkenes with CO_(2) via catalytic electron donor-acceptor(EDA)complex activation.A variety of oxindole-3-acetic acid and derivatives were generated in moderate to excellent yields from N-arylacrylamides and CO_(2).Mechanistic studies revealed the formation of an EDA complex between catalytic thiolate and alkene.Notably,this redox-neutral reaction features mild,transition-metal and photocatalyst-free conditions,good functional group tolerance and broad substrate scope.Furthermore,the facile synthesis of key intermediates in natural products underscores the utility of this methodology.
基金supported by the National Natural Science Foundation of China(22071159)Sichuan Science and Technology Program(2018JY560)。
文摘Isofunctional reactions involving the cleavage of carbon-carbon double bonds(C=C)hold an important position in organic synthesis,as they allow for the restructuring of alkene carbon chains and enable the exchange of functional groups without introducing exogenous groups.Currently,these reactions are primarily divided into C=C/C=C metathesis and C=C/C=O metathesis,with most relying on the use of transition metal catalysts.We report herein a C=C/CH_(2) metathesis reaction that obviates the need for transition metals and directing groups,and is characterized by economic and straightforward operation.This reaction not only facilitates the replacement of nitriles with ketones,but also enables the replacement of ketones with nitriles,demonstrating great universality.
基金supported by the National Natural Science Foundation of China(21772052,21772053,21772129,21801176,21672099,21732003)Chinese Academy of Sciences(XDB20020200)
文摘In recent years, visible light-driven organic photochemical synthesis has attracted wide research interest from academic and industrial communities due to its features of green and sustainable chemistry. In this flourishing area, Chinese chemists have devoted great efforts to different aspects of synthetic chemistry. This review will summarize their representative work according to the following categories: C–H functionalization, synthesis of aromatic aza-heterocycles, asymmetric organic photochemical synthesis, transformations of small molecules and biomolecule-compatible reactions.
基金supported by the National Natural Science Foundation of China(21801176,91956111)the Sichuan Science and Technology Program(2019YJ0379,20CXTD0112)the Fundamental Research Funds for the Central Universities。
文摘Carbon dioxide(CO2)is an important and appealing C1 building block in chemical synthesis due to its nontoxicity,abundance,availability and sustainability.Tremendous progress has been achieved in the chemical transformation of CO2 into high valueadded organic chemicals.However,the asymmetric synthesis with CO2 to form enantioenriched molecules,especially the catalytic process,has lagged far behind.The enantioselective incorporation of CO2 into organic compounds is highly desirable,as the corresponding chiral products,such as carboxylic acids and amino acids,are common structural units in a vast array of natural products and biologically active compounds.Herein,we discuss recent progress toward the enantioselective incorporation of CO2 into organic molecules,which mainly rely on three strategies:1)kinetic resolution or desymmetrization of epoxides with CO2 to form chiral cyclic carbonates and polycarbonates;2)nucleophilic attack of O-or N-nucleophiles to CO2 in tandem with asymmetric C–O bond formation to prepare chiral cyclic carbonates and carbamates;3)direct enantioselective nucleophilic attack of organometallic reagents to CO2 with asymmetric C–C bond formation.Finally,challenges and future outlook in this area are also presented.
基金supported by the National Natural Science Foundation of China(21772129,21801176)the The National Basic Research Program of China from the Minstry of Science and Technology of China(2015CB856600)+2 种基金Sichuan Science and Technology Program(2019YJ0379)Neijiang Normal University(KF10076)the Fundamental Research Funds for the Central Universities(YJ201516)
文摘Herein we report a novel visible-light-mediated external reductant-free reductive cross coupling for the construction of C sp2–C sp3 bonds.A variety of benzylammonium salts underwent selective coupling with(hetero)aryl nitriles to deliver important diarylmethanes under mild reaction conditions.Importantly,photocatalysts can be omitted for many cases,which might involve the electron donor acceptor(EDA)complex.Mechanistic studies indicated benzylic radicals might be involved as the key intermediates.Moreover,the in situ generated NMe3 via cleavage of C–N bond in ammonium salts acts as the electron donor,thus avoiding the use of external-reductant.
文摘Herein, we report a novel synthesis of 1,3-oxazin-6-ones from enamides with CO2 through C--H carboxylation and one-pot cyclization. This transition-metal-free and redox-neutral process features broad substrate scope, good functional group tolerance and facile product derivatization. The nucleophilic attack to CO2 from the electron-rich alkene is demonstrated for this reaction.
基金We thank the financial support from the National Natural Science Foundation of China(Nos.21775107,21822108)the Sichuan Science and Technology Program(20CXTD0112)the Fundamental Research Funds for the Central Universities.
文摘Prediction of reaction yields using machine learning(ML)can help chemists select high-yielding reactions and provide prior experience before wet-lab experimenting to improve efficiency.However,the exploration of a multicomponent organic reaction features many complex variables and limited number of experimental data,which are challenging for the application of ML.Herein,we perform yield prediction for the synthesis of 2-oxazolidones via Cu-catalyzed radical-type oxy-alkylation of allylamines and herteroaryl-methylamines with CO_(2),which is a three-component reaction.Using physicochemical descriptors as features to launch ML modelling,we find that XGBoost shows significantly improved performance over linear models and these features are effective for the yield prediction.Moreover,out-of-sample prediction indicates the application potential of the model.This study demonstrates great potential of regression-modelling-based ML in organic synthesis even with complex factors and a general small size of reaction data,which are generated from the classical research pattern of method for the inquiry of multicomponent reactions.
文摘Summary of main observation and conclusion A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C-O activation of enolates was developed.Besides ketones,aldehydes were also suitable substrates for the presented catalytic system to produce di-or tri-substituted olefins.It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols,which could not survive in other reported routes for converting carbonyl compounds to olefins.This method also showed good regio-and stereo-selectivity for olefin products.Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C-O activation of enolates,thus offering helpful contribution to current enol chemistry.
基金the financial support from the National Natural Sci ence Foundation of China(Nos.21772135,21871195,21822108)the Fok Ying Tung Education Foundation(161013)+1 种基金the"973"Pro-ject from the MOST of China(No.2015CB856600)the Fun damental Research Funds for the Central Universities.We also thank the comprehensive training platform of the Specialized Laboratory in the College of Chemistry at Sichuan University for compound testing.
文摘Summary of main observation and conclusion The radical-initiated carboxylativecyclization of allylamines with CO_(2)represents an efficientand highly promising strategy to afford valuable 2-oxazolidinones.However,the radical precursorsand pathways to generate radicals in such processes are still lim-ited.Herein,we report the firstCu-catalyzed selective oxy-cyanoalkylation of allylamines with cycloketone oxime esters and CO_(2)viaC-C bond cleavage.Many cyanoalkyl-substituted 2-oxazolidinones are obtained in moderate togood yields withhigh regio-and chemo-selectivities.The utility ofthis re-dox-neutral and cyanide-free method is demonstrated with mild conditions,broad substrate scope,good functional group tolerance and easy scalability.
基金Financial support was provided by the the National Natural Science Foundation of China(nos.21822108,21822303,21801176,21772129,and 21772020)the Fok Ying Tung Education Foundation(no.161013)+1 种基金Sichuan Science and Technology Program(nos.2019YJ0379 and 20CXTD0112)the Fundamental Research Funds for the Central Universities.
文摘Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.
基金supported by the National Natural Science Foundation of China(21822108,21772129)the Fok Ying Tung Education Foundation(161013)+1 种基金Sichuan Science and Technology Program(20CXTD0112)Fundamental Research Funds for the Central Universities。
文摘Herein,we report a novel protocol for visible-light-driven alkylative carboxylation of alkenes with CO_(2) in the absence of external photocatalyst.Under the irradiation of visible light,a variety of 4-alkyl-1,4-dihydropyridines(alkyl-DHPs)serve as not only alkyl radical precursors but also photoexcited reductants probably with the potential to reduce benzyl radicals.Several styrenes and acrylates are applicable in this reaction to give structurally diverse carboxylic acids in good to excellent yields.These reactions feature mild reaction conditions(1 atm of CO_(2),room temperature,visible light,photocatalyst-and transition metalfree),good functional group tolerance,easy scalability,as well as high regio-,and chemo-selectivity.Mechanistic investigations provide evidence that alkyl radical,benzyl radical and carbanion might be involved in this reaction,providing a novel strategy for CO_(2) utilization.
基金supported by the National Natural Science Foundation of China(22225106,22201027)the Fundamental Research Funds for the Central Universities。
文摘Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In contrast to the well-developed functionalization of one carbon fragment after C–C bond cleavage,herein,we report a novel electro-reductive carboxylation of C(sp^(3))–C(sp^(3))bond in multi-aryl ethanes with carbon dioxide(CO_(2))by utilizing both carbon fragments.Thus,this reaction exhibits an atom-,step-economic approach for the synthesis of carboxylic acids,fulfilling principal aspirations of organic synthesis.Moreover,this method features mild reaction conditions,broad substrate scope,and good functional group tolerance.Symmetric and asymmetric substrates bearing primary,secondary,or tertiary C(sp^(3))–C(sp^(3))bonds are all amenable to this strategy,enabling one or two structurally different carboxylic acids to be facilely constructed at the same time.Mechanistic investigations indicate that carbanions might be the key intermediates in this reaction,which could be captured by CO_(2)efficiently.
