Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups in...Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.展开更多
Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, an...Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.展开更多
As an essential part of the performance improvement of lithium metal batteries,the acquisition of dense(LiF-rich solid electrolyte interphase(SEI))has always been an urgent problem to be solved.Herein,we synthesized Z...As an essential part of the performance improvement of lithium metal batteries,the acquisition of dense(LiF-rich solid electrolyte interphase(SEI))has always been an urgent problem to be solved.Herein,we synthesized Zeolitic Imidazolate Frameworks(ZIFs)modified by two different functional groups(-NH_(2),-CH_(3))and used them as the fillers of polyethylene oxide(PEO)composite solid electrolytes to explore the catalytic effect of groups on LiF generation at the Li/electrolytes interface.In a LiFePO 4||SPE||Li cell test,the PEO-ZIF-NH_(2)with LiF-rich SEI exhibits enhanced cycling performance,which was 3.8 times longer than that of PEO-ZIF-CH_(3).The formation mechanism of LiF-rich SEI was investigated using first-principles calculation,revealing that ZIFs-NH_(2)makes the C-F bond in TFSI-longer compared with ZIFs-CH_(3),which leads to easier breakage of the C-F bond and promoted the formation of LiF.The simple design idea of using organic catalysis to generate more stable SEI provides a new aspect for preparing high-performance lithium metal batteries.展开更多
The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guani...The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly thermodynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers： △H（Sol） = △H（SCF） ＋ △G（Solv）, which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.展开更多
An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reacti...An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reaction proceeded efficiently in an undivided cell without the use of a stoichiometric chemical oxidant.In addition to the previously established synthesis ofβ-hydroxysulfones in the presence of water,minor modification of this protocol by using either external alcohol nucleophiles or internal carboxylic acid nucleophile also led to the synthesis ofβ-alkoxysulfones,andβ-sulfonyl lactones.展开更多
Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition ...Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition metal catalysis,the employment of cheap,abundant aryl chlorides as coupling partner is still a challenging task in this field.Herein,we report our first achievement in 1,1-difunctionalization of alkenes with aryl chlorides as coupling partners.The success is predominantly ascribed to the judicious selection of 1,2-diamine ligand.This study provides an efficient protocol for the synthesis of secondary benzyl boronates from easily accessible feedstock chemicals.Furthermore,the distinguished features of this method include excellent 1,1-regio-and chemoselectivity,good functional group tolerance and easily-operational catalytic reaction conditions.展开更多
An efficient and practical electrochemical method for the three-component reaction cascade Mumm rearrangement of imides has been developed using a simple undivided cell with carbon electrodes at room temperature,which...An efficient and practical electrochemical method for the three-component reaction cascade Mumm rearrangement of imides has been developed using a simple undivided cell with carbon electrodes at room temperature,which provides a useful strategy for the rapid synthesis of sulfur-containing imides with broad substrate scope and high functional tolerance.It is a rare example of in situ generation of O-acyl isoamide precursor for Mumm rearrangement.展开更多
The development of carbon dioxide(CO_(2))capture and utilization is of vital importance.However,previous photocatalytic reduction reactions for converting CO_(2)into chemicals(e.g.,CO,HCOOH,CH_(4),or CH_(3)OH)rely hea...The development of carbon dioxide(CO_(2))capture and utilization is of vital importance.However,previous photocatalytic reduction reactions for converting CO_(2)into chemicals(e.g.,CO,HCOOH,CH_(4),or CH_(3)OH)rely heavily on sacrificial reagents.Herein,we disclose a visible light photoredox-catalyzed 1,2-difunctionalization of terminal alkynes by using CO_(2)as an ideal quenching reagent and the xanthene dye Rhodamine 6G(Rh-6G)as a photocatalyst(PC)via consecutive photoinduced electron transfer(ConPET)process.The newly developed CO_(2)-triggered reaction provides a highly regio-and stereo-selective approach to diverse functionalized(E)-α-vinylsulfones with simultaneously efficient conversion of CO into oxalate.The practicality of this protocol is demonstrated by late-stage modification of alkynes derived from biologically active natural products or drugs.Preliminary mechanistic studies suggest that the homocoupling of CO_(2) radical anion results in the formation of oxalate.展开更多
A highly efficient and green four-component difunctionalization of styrenes with KSCN and imidazo[1,2-a]pyridines was developed.In this protocol,readily available KSCN was used as a sulfur source and inexpensive K2S2O...A highly efficient and green four-component difunctionalization of styrenes with KSCN and imidazo[1,2-a]pyridines was developed.In this protocol,readily available KSCN was used as a sulfur source and inexpensive K2S2O8 was used as a free radical initiator.A series of C-3 thiolated imidazopyridine analogues were synthesized,in which hydroxyl group and aryl or alkyl group were incorporated.A novel method for the synthesis of multifunctionalized imidazopyridines was established.展开更多
Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summ...Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summarized comprehensively the recent literature reports on the electrochemical oxidative difunctionalization of unsaturated C—C bonds. The reaction types described in this review included electrochemical intermolecular cyclization, electrochemical intramolecular cyclization, and electrochemical difunctionalization of alkenes/alkynes. This review focuses on the discussion of its synthetic generality for the preparation of functionalized compounds and the related electrochemical oxidative reaction mechanism.展开更多
Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry.They allow for the development of diverse reaction modes with enhance...Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry.They allow for the development of diverse reaction modes with enhanced efficiency and structural variability,which is in high demand for atom-economic and sustainable synthesis.Among them,bifunctional reagents containing Nheteroaryl groups have received much attention due to their ability to introduce privileged N-heteroaryl moieties into complex molecules that are otherwise challenging to access.Furthermore,these reagents have been employed under visible-light conditions to achieve various synthetic applications,enabling difunctionalization of alkenes,alkynes,and[1.1.1]propellanes under mild reaction conditions,providing access to highly functionalized N-heteroarenes.In this review,we provide an overview of the recent achievements and applications of photoinduced difunctionalization using bifunctional reagents containing N-heteroaryl groups.We systematically categorize the representative contributions in the field based on bifunctional reagents and their reactivity patterns.This review aims to highlight the potential of these reagents as powerful synthetic tools for sustainable and diverse synthesis.展开更多
Here,we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity.This difu...Here,we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity.This difunctionalization reaction could undergo smoothly using 1 mol%catalyst loading with good functional group tolerance.Not only di-and tri-substituted hydrosilanes,but also alkoxysilane is suitable,which does explore the scope of the family of 1-amino-2-silyl compounds.The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time via absorption spectral analysis in this one-pot,two-step transformations.The primary mechanism has been proposed based on the control experiments.展开更多
A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo-and stereoselectivity. Preliminary...A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo-and stereoselectivity. Preliminary mechanistic studies indicated that the reaction probably underwent a Cu-catalyzed formal C–H insertion to produce an allene intermediate, which was then trapped by a sulfonyl anion to give the corresponding product.展开更多
Tremendous progress has been made on aromatic fusion of acenaphthylene towards organic semiconductors.However,scarce studies focus on the functionalization of acenaphthylene without resort to aromatic extension,althou...Tremendous progress has been made on aromatic fusion of acenaphthylene towards organic semiconductors.However,scarce studies focus on the functionalization of acenaphthylene without resort to aromatic extension,although vinylene double bond is highly reactive ascribed to the ring strain of the fused cyclopentene.Herein,for the first time we employ copper-promoted domino cyanation/Ullmann coupling to achieve a series of difunctionalized acenaphthylene imides(ANIs)with varied optoelectronic properties.Both Ullmann homocoupling and crosscoupling can be combined with cyanation for difunctionalization of ANIs.The introduction of cyano groups influences oppositely not only the energy levels but also the antiaromaticity of the fivemembered rings in ANIs relative to the dimethylamino substituent due to the electron donating or withdrawing effects.By altering the functional units,the optical and electrical characteristics have been tailored rationally;thus p,n or ambipolar semiconducting properties can be achieved for the ANI derivatives.This article opens up possibilities to the development of organic semiconducting materials based on ANIs without aromatic extension,which is promising for applications in organic electronics.展开更多
Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difu...Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.展开更多
Indole and its derivatives represent the most important heterocycles that are widely present in bioactive molecules,natural products and advanced materials,and thus functionalization of simple indoles to construct com...Indole and its derivatives represent the most important heterocycles that are widely present in bioactive molecules,natural products and advanced materials,and thus functionalization of simple indoles to construct complex indole derivatives is a research area of great current interest.2,3-Difunctionalization of indoles has been extensively studied,but the reported examples are limited to the synthesis of 2,3-disubstituted indole derivatives or dearomatized products containing central chirality.Until now,atroposelective 2,3-difunctionalization of simple indoles for the synthesis of axially chiral molecules is unknown.In this article,we report a straightforward and general strategy for atroposelective 2,3-difunctionalization of simple indoles,forming indole-containing axially chiral products in good yields and excellent enantioselectivities.The strategy we introduce herein may lead to the discovery of new approaches for multifunctionalization of indoles and other heterocyclic scaffolds,thus accessing novel axially chiral heteroarene-containing scaffolds that may find applications in medicinal chemistry and asymmetric catalysis.展开更多
Efficiently modifying glycals by directly introducing functional groups into their double bonds is a longstanding challenge.Here,the strategy of introducing two different functional groups into 1-iodoglycals to obtain...Efficiently modifying glycals by directly introducing functional groups into their double bonds is a longstanding challenge.Here,the strategy of introducing two different functional groups into 1-iodoglycals to obtain modified glycals in one step through palladium catalysis was reported for the first time,and the modified glycals contained stereodefined tetrasubstituted olefins.Using this method,various difunctionalized glycals that were difficult to form by other routes were synthesized in moderate to good yields.Control experiments and density functional theory calculations show that the palladium catalyst played dual roles in this transformation,namely,inducing nucleophilic substitution and catalyzing Suzuki coupling.The reaction intermediate was isolated and confirmed by X-ray crystallographic analysis.Furthermore,the gram-scale synthesis and facile deprotection of the target compound enhances the practicality of this strategy.展开更多
A practical method for the 1,3-azidoheteroarylation of[1.1.1]propellane with cyclic aldimines and azidotrimethylsilane(TMSN_(3))is presented.A broad spectrum of 1-azido-3-heteroaryl bicyclo[1.1.1]pentanes(BCPs)can be ...A practical method for the 1,3-azidoheteroarylation of[1.1.1]propellane with cyclic aldimines and azidotrimethylsilane(TMSN_(3))is presented.A broad spectrum of 1-azido-3-heteroaryl bicyclo[1.1.1]pentanes(BCPs)can be synthesized in moderate-to-good yields under standard conditions.The versatility of this method is further confirmed by its applicability to large-scale synthesis,product derivatizations,and late-stage functionalization of pharmaceutically relevant molecules.Mechanistic studies reveal that a radical relay mechanism initiated by a single-electron transfer(SET)process is operational.展开更多
The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds.The existing approach is extensively promoted by using C/Xcentered radicals a...The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds.The existing approach is extensively promoted by using C/Xcentered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes.In contrast,2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals(NCRs) and nucleophiles still remains rarely underexplored.It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes.Herein,we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles(NuH) in high yields and with high regioselectivity.This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required.This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride,ammonia,water,alcohols,and acids which enables the formation of C-N and C-X(X=F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination,diamination and oxoamination of alkenes.展开更多
文摘Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.
基金supported by Zhejiang Provincial Natural Science Foundation of China(LR19B020001)the National Natural Science Foundation of China(21472162,21772171)the National Basic Research Program of China(2015CB856600)~~
文摘Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.
基金This work was financially supported by the National Natural Science Foundation of China(No.11872054)the Natural Science Foundation of Hunan Province(Nos.2020JJ5530,2020JJ2026,and 2021JJ30643)the Science and Technology Innovation Project of Hunan Province(No.2018RS3091).
文摘As an essential part of the performance improvement of lithium metal batteries,the acquisition of dense(LiF-rich solid electrolyte interphase(SEI))has always been an urgent problem to be solved.Herein,we synthesized Zeolitic Imidazolate Frameworks(ZIFs)modified by two different functional groups(-NH_(2),-CH_(3))and used them as the fillers of polyethylene oxide(PEO)composite solid electrolytes to explore the catalytic effect of groups on LiF generation at the Li/electrolytes interface.In a LiFePO 4||SPE||Li cell test,the PEO-ZIF-NH_(2)with LiF-rich SEI exhibits enhanced cycling performance,which was 3.8 times longer than that of PEO-ZIF-CH_(3).The formation mechanism of LiF-rich SEI was investigated using first-principles calculation,revealing that ZIFs-NH_(2)makes the C-F bond in TFSI-longer compared with ZIFs-CH_(3),which leads to easier breakage of the C-F bond and promoted the formation of LiF.The simple design idea of using organic catalysis to generate more stable SEI provides a new aspect for preparing high-performance lithium metal batteries.
基金This work was supported by the Science Foundation of Jinan University (639)
文摘The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly thermodynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers： △H（Sol） = △H（SCF） ＋ △G（Solv）, which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.
基金Financial support was provided by Hong Kong RGC (No. 16302318)Shenzhen Science and Technology Innovation Committee (No. JCYJ20170818113708560)HKUST (No. IEG17SC03)
文摘An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reaction proceeded efficiently in an undivided cell without the use of a stoichiometric chemical oxidant.In addition to the previously established synthesis ofβ-hydroxysulfones in the presence of water,minor modification of this protocol by using either external alcohol nucleophiles or internal carboxylic acid nucleophile also led to the synthesis ofβ-alkoxysulfones,andβ-sulfonyl lactones.
基金supported by grants from the National Natural Science Foundation of China(No.22122107)the Fundamental Research Funds for Central Universities(No.2042021kf0190).
文摘Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition metal catalysis,the employment of cheap,abundant aryl chlorides as coupling partner is still a challenging task in this field.Herein,we report our first achievement in 1,1-difunctionalization of alkenes with aryl chlorides as coupling partners.The success is predominantly ascribed to the judicious selection of 1,2-diamine ligand.This study provides an efficient protocol for the synthesis of secondary benzyl boronates from easily accessible feedstock chemicals.Furthermore,the distinguished features of this method include excellent 1,1-regio-and chemoselectivity,good functional group tolerance and easily-operational catalytic reaction conditions.
基金support from the Science and Technology Innovation Program of Hunan Province(No.2021RC2079)China Postdoctoral Science Foundation(Nos.2022T150075 and 2022M720541)+2 种基金Hunan Provincial Department of Education Outstanding Youth Project(No.22B0212)Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project(No.TSBI-CIP-CXRC-038)National College Students Innovation and Entrepreneurship Training Program(No.S202210537024).
文摘An efficient and practical electrochemical method for the three-component reaction cascade Mumm rearrangement of imides has been developed using a simple undivided cell with carbon electrodes at room temperature,which provides a useful strategy for the rapid synthesis of sulfur-containing imides with broad substrate scope and high functional tolerance.It is a rare example of in situ generation of O-acyl isoamide precursor for Mumm rearrangement.
基金supported by the National Natural Science Foundation of China(Nos.22471045,U2001222)the Science and Technology Planning Project of Guangdong Province(No.2021A0505030069)。
文摘The development of carbon dioxide(CO_(2))capture and utilization is of vital importance.However,previous photocatalytic reduction reactions for converting CO_(2)into chemicals(e.g.,CO,HCOOH,CH_(4),or CH_(3)OH)rely heavily on sacrificial reagents.Herein,we disclose a visible light photoredox-catalyzed 1,2-difunctionalization of terminal alkynes by using CO_(2)as an ideal quenching reagent and the xanthene dye Rhodamine 6G(Rh-6G)as a photocatalyst(PC)via consecutive photoinduced electron transfer(ConPET)process.The newly developed CO_(2)-triggered reaction provides a highly regio-and stereo-selective approach to diverse functionalized(E)-α-vinylsulfones with simultaneously efficient conversion of CO into oxalate.The practicality of this protocol is demonstrated by late-stage modification of alkynes derived from biologically active natural products or drugs.Preliminary mechanistic studies suggest that the homocoupling of CO_(2) radical anion results in the formation of oxalate.
文摘A highly efficient and green four-component difunctionalization of styrenes with KSCN and imidazo[1,2-a]pyridines was developed.In this protocol,readily available KSCN was used as a sulfur source and inexpensive K2S2O8 was used as a free radical initiator.A series of C-3 thiolated imidazopyridine analogues were synthesized,in which hydroxyl group and aryl or alkyl group were incorporated.A novel method for the synthesis of multifunctionalized imidazopyridines was established.
文摘Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summarized comprehensively the recent literature reports on the electrochemical oxidative difunctionalization of unsaturated C—C bonds. The reaction types described in this review included electrochemical intermolecular cyclization, electrochemical intramolecular cyclization, and electrochemical difunctionalization of alkenes/alkynes. This review focuses on the discussion of its synthetic generality for the preparation of functionalized compounds and the related electrochemical oxidative reaction mechanism.
基金supported by the Institute for Basic Science(IBS-R010-A2)。
文摘Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry.They allow for the development of diverse reaction modes with enhanced efficiency and structural variability,which is in high demand for atom-economic and sustainable synthesis.Among them,bifunctional reagents containing Nheteroaryl groups have received much attention due to their ability to introduce privileged N-heteroaryl moieties into complex molecules that are otherwise challenging to access.Furthermore,these reagents have been employed under visible-light conditions to achieve various synthetic applications,enabling difunctionalization of alkenes,alkynes,and[1.1.1]propellanes under mild reaction conditions,providing access to highly functionalized N-heteroarenes.In this review,we provide an overview of the recent achievements and applications of photoinduced difunctionalization using bifunctional reagents containing N-heteroaryl groups.We systematically categorize the representative contributions in the field based on bifunctional reagents and their reactivity patterns.This review aims to highlight the potential of these reagents as powerful synthetic tools for sustainable and diverse synthesis.
基金Financial supports were provided by the National Key R&D Program of China(2021YFA1500200 and 2021YFF0701600)the NSFC(22271249)the Fundamental Research Funds for the Central Universities(226-2022-00224 and 226-2023-00115).
文摘Here,we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity.This difunctionalization reaction could undergo smoothly using 1 mol%catalyst loading with good functional group tolerance.Not only di-and tri-substituted hydrosilanes,but also alkoxysilane is suitable,which does explore the scope of the family of 1-amino-2-silyl compounds.The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time via absorption spectral analysis in this one-pot,two-step transformations.The primary mechanism has been proposed based on the control experiments.
基金supported by the National Natural Science Foundation of China(21432009,21672200,21472177,21772185,21801233)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)
文摘A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo-and stereoselectivity. Preliminary mechanistic studies indicated that the reaction probably underwent a Cu-catalyzed formal C–H insertion to produce an allene intermediate, which was then trapped by a sulfonyl anion to give the corresponding product.
基金supported by the Fundamental Research Funds for the Central Universities(buctrc202103,buctrc202128)the National Natural Science Foundation of China(21975263,22171019,52103200)+4 种基金SINOPEC(222131)the Open Project Program of Wuhan National Laboratory for Optoelectronics(2021WNLOKF005)the State Key Laboratory of Fine Chemicals(KF2201,Dalian University of Technology)the State Key Laboratory of Luminescent Materials and Devices(2022skllmd-14)the State Key Laboratory of Supramolecular Structure and Materials(SKLSSM2022036)。
文摘Tremendous progress has been made on aromatic fusion of acenaphthylene towards organic semiconductors.However,scarce studies focus on the functionalization of acenaphthylene without resort to aromatic extension,although vinylene double bond is highly reactive ascribed to the ring strain of the fused cyclopentene.Herein,for the first time we employ copper-promoted domino cyanation/Ullmann coupling to achieve a series of difunctionalized acenaphthylene imides(ANIs)with varied optoelectronic properties.Both Ullmann homocoupling and crosscoupling can be combined with cyanation for difunctionalization of ANIs.The introduction of cyano groups influences oppositely not only the energy levels but also the antiaromaticity of the fivemembered rings in ANIs relative to the dimethylamino substituent due to the electron donating or withdrawing effects.By altering the functional units,the optical and electrical characteristics have been tailored rationally;thus p,n or ambipolar semiconducting properties can be achieved for the ANI derivatives.This article opens up possibilities to the development of organic semiconducting materials based on ANIs without aromatic extension,which is promising for applications in organic electronics.
基金supported by the National Natural Science Foundation of China (21871211, 21774029, 22122107)the Fundamental Research Funds for Central Universities (2042019kf0208)。
文摘Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.
文摘Indole and its derivatives represent the most important heterocycles that are widely present in bioactive molecules,natural products and advanced materials,and thus functionalization of simple indoles to construct complex indole derivatives is a research area of great current interest.2,3-Difunctionalization of indoles has been extensively studied,but the reported examples are limited to the synthesis of 2,3-disubstituted indole derivatives or dearomatized products containing central chirality.Until now,atroposelective 2,3-difunctionalization of simple indoles for the synthesis of axially chiral molecules is unknown.In this article,we report a straightforward and general strategy for atroposelective 2,3-difunctionalization of simple indoles,forming indole-containing axially chiral products in good yields and excellent enantioselectivities.The strategy we introduce herein may lead to the discovery of new approaches for multifunctionalization of indoles and other heterocyclic scaffolds,thus accessing novel axially chiral heteroarene-containing scaffolds that may find applications in medicinal chemistry and asymmetric catalysis.
基金We thank the National Natural Science Foundation of China(NSF 22171114 and 21772075)for its financial support.
文摘Efficiently modifying glycals by directly introducing functional groups into their double bonds is a longstanding challenge.Here,the strategy of introducing two different functional groups into 1-iodoglycals to obtain modified glycals in one step through palladium catalysis was reported for the first time,and the modified glycals contained stereodefined tetrasubstituted olefins.Using this method,various difunctionalized glycals that were difficult to form by other routes were synthesized in moderate to good yields.Control experiments and density functional theory calculations show that the palladium catalyst played dual roles in this transformation,namely,inducing nucleophilic substitution and catalyzing Suzuki coupling.The reaction intermediate was isolated and confirmed by X-ray crystallographic analysis.Furthermore,the gram-scale synthesis and facile deprotection of the target compound enhances the practicality of this strategy.
基金Project supported by the Natural Science Foundation of Zhejiang Province(No.LMS25B060007)。
文摘A practical method for the 1,3-azidoheteroarylation of[1.1.1]propellane with cyclic aldimines and azidotrimethylsilane(TMSN_(3))is presented.A broad spectrum of 1-azido-3-heteroaryl bicyclo[1.1.1]pentanes(BCPs)can be synthesized in moderate-to-good yields under standard conditions.The versatility of this method is further confirmed by its applicability to large-scale synthesis,product derivatizations,and late-stage functionalization of pharmaceutically relevant molecules.Mechanistic studies reveal that a radical relay mechanism initiated by a single-electron transfer(SET)process is operational.
基金the National Science Foundation of China(No.22071058)the Fundamental Research Funds for the Central Universities for financial support。
文摘The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds.The existing approach is extensively promoted by using C/Xcentered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes.In contrast,2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals(NCRs) and nucleophiles still remains rarely underexplored.It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes.Herein,we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles(NuH) in high yields and with high regioselectivity.This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required.This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride,ammonia,water,alcohols,and acids which enables the formation of C-N and C-X(X=F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination,diamination and oxoamination of alkenes.
