A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly ...A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly functionalized 2-cyanopyrroles are constructed efficiently through a new formal [3 + 2] mode, demonstrating diverse reactivity and synthetic utility in organic chemistry. 2-Cyanopyrrole is converted into a nucleobase analogue of Remdesivir and 5H-pyrrolo[2,1-a]isoindole through a three-step or a two-step sequence, respectively. This protocol features broad substrate scope, operational simplicity and good functional group tolerance.展开更多
The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed ...The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp＊Mo（CO）2（=SiMe2）（SiMe3） Si-C bond were investigated extensively by using the DFT method.The effective core potentials（ECP） with a double-ζ valence basis set（LanL2DZ） were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si（ζd = 0.262）,C（ζd = 0.8） and N（ζd = 0.8）.The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.展开更多
The reactive intermediate generated by the addition of alkyl isocyanides to dialkyl acetylenedicarboxylate was trapped by 6- quinolinol to produce highlyfunctionalized 4H-chromenes in fairly good yields.
The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
An efficient 1-methylimidazole-catalyzed synthesis of dialkyl 2-[（4-methylphenyl）sulfonyl]-1H-pyrrole-3,4-dicarboxylates is described.The reactive 1：1 zwitterionic intermediate formed by the addition of 1-methylimi...An efficient 1-methylimidazole-catalyzed synthesis of dialkyl 2-[（4-methylphenyl）sulfonyl]-1H-pyrrole-3,4-dicarboxylates is described.The reactive 1：1 zwitterionic intermediate formed by the addition of 1-methylimidazole to dialkyl acetylenedicarboxylates is trapped by tosylmethyl isocyanide（TOSMIC） to afford the title compounds in excellent yields.展开更多
The reaction between 2-aminobenzothiazole with dialkyl acetylenedicarboxylates in the presence of isocyanides,leads to functionalized azadienes in good yields.
A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into ...A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into the C–Cu bond of organocuprate intermediate is involved for the formation of the sevenmembered azepinone ring.展开更多
The addition of pyridine-2-carboxaldoxime or α-furildioxime to dialkyl acety lenedicarboxy lates under neutral conditions in the presence of alkyl isocyanides leads to ketenimines and bis（ketenimines） in good yields.
A palladium-catalyzed formal[2+2+1]cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein.The transformation worked well to produce a series of 7 H-acenaphtho[1,2-b]pyrrole with a broad...A palladium-catalyzed formal[2+2+1]cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein.The transformation worked well to produce a series of 7 H-acenaphtho[1,2-b]pyrrole with a broad reaction scope.Isocyanides play a dual role in the reaction.One is a C1 building block,and another is used as C1 N1 component.In the process,the[2+2+1]cyclization involves imidoylation,regioselective addition of imidoylpalladium species into alkyne,double imidoylation,and another addition of the resulting imidoylpalladium species into imine bonds.展开更多
In this study,a new twisting gold（Ⅰ） isocyanide complex based on tetraphenylethene（TPE）,TPE-NC-Au.was designed and synthesized.It exhibits aggregation induced phosphorescence（AIP） characteristics,owing to the i...In this study,a new twisting gold（Ⅰ） isocyanide complex based on tetraphenylethene（TPE）,TPE-NC-Au.was designed and synthesized.It exhibits aggregation induced phosphorescence（AIP） characteristics,owing to the incorporation of Au moiety and conformation rigidification in the aggregated states.Moreover,the emission color of the crystalline solid of TPE-NC-Au changes from blue（454 nm） to green（500 nm） in response to mechanical grinding,due to the combined effects of conformation planarization,enhanced π…π stacking,as well as the emergence of aurophilic interactions in the ground amorphous state.Notably,the emission color can be restored upon solvent fuming,associating with the reconstruction of crystalline lattices.The AIP and switchable mechanochromism of TPE-NC-Au make it suitable for potential applications in bioimaging,sensing,and optoelectronic devices.展开更多
With the exploration of novel sustainable protocol for functional polyamides'(PAs)construction as the starting point,herein,the small molecular model compound(M 1-ssBIC)was prepared firstly by manual grinding of m...With the exploration of novel sustainable protocol for functional polyamides'(PAs)construction as the starting point,herein,the small molecular model compound(M 1-ssBIC)was prepared firstly by manual grinding of monofunctional benzoxazine(1a)and isocyanide(1 b)via solid-state benzoxazine-isocyanide chemistry(ssBIC)to evaluate the feasibility of ssBIC.Linear PAs(P1-series polymers)were subsequently synthesized from biunctional benzoxazine(2a)and isocyanide(2b),and the influence of the loading of catalyst(octylphosphonic acid)(OPA)on the polymerization was investigated.Afterwards,two kinds of cross-linked PAs were successfully constructed via ssBIC by using trifunctional benzoxazine(3a)and cross-linked polybenzoxazine(4a)as reaction substrates,respectively,thus verifying the adaptability of ssBIC.Structural characterization indicates that amide,phenolic hydroxyl and tertiary amine substructures,with metal-complexing capability,have been successfully integrated into the obtained PAs.A type of representative PA/silver composite(P3-AgNPs)was prepared subsequently via in situ reduction treatment,and its application as recyclable reduction catalyst for organic pollutant p-nitrophenol(4-NP)was preliminarily investigated here to provide the example for possible downstream application of ssBIC.We think that this current work could provide a new pathway for the construction of functional PAs through facile and sustainable ssBIC protocol.展开更多
A manganese (Ⅲ)-promoted oxidative radical cascade reaction of easily accessible arylboronic acids with isocyanides to construct diimide derivatives was studied. This protocol provides a new way to synthesis of acety...A manganese (Ⅲ)-promoted oxidative radical cascade reaction of easily accessible arylboronic acids with isocyanides to construct diimide derivatives was studied. This protocol provides a new way to synthesis of acetyl diimide derivatives. New C-C, C-N and C=O bonds were formed in one step.展开更多
Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr =...Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr = 547.66, space group P1, a = 8.6448(1), b = 11.5772(2), c = 14.6666(4) ?, α = 88.387(2), β = 86.826(2), γ = 68.222(1)°, V = 1360.97(5) ?3, Z = 2, F(000) = 568, Dc = 1.336 g/cm3, μ = 1.582 mm-1, the final R = 0.0629 and wR = 0.1282 for 3257 observed reflections with I > 2σ(I). The phenylacetylide adopts μ-η1 and μ3-η1,η1,η2 bonding modes. The compound shows intense luminescence in the solid state.展开更多
A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad re...A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad reaction scope.Based on mechanism studies,it is believed that the palladiumcatalyzed [4+1] imidoylative cycloaddition of prop-2-yn-1-ones was concerted.Treated with a ryl amine and H_2 O,the [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides provided 2-amino-4-amidylpyrroles efficiently.展开更多
The adsorption of CH3CN and CH3NC on the Pt（lll） surface at the 1/4 monolayer （ML） coverage has been car-ried out at the level of density functional theory for understanding hydrogenation processes of nitriles. Th...The adsorption of CH3CN and CH3NC on the Pt（lll） surface at the 1/4 monolayer （ML） coverage has been car-ried out at the level of density functional theory for understanding hydrogenation processes of nitriles. The most favored ad-sorption structure for CH3 CN is the C--N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms. For CH3NC, the most stable configuration is the CH3 NC locates at the face center cubic （fcc） site with the C-atom bonded to three Pt atoms. In addition, the HCN and HNC adsorption has been computed, and the adsorption pattern is nearly similar to the CH3CN and CH3NC, respectively. The adsorbed molecules rehybridize on the surface, be-coming non-linear with a bent C-C-N or C-N-C angle. Furthermore, the binding mechanism of these molecules on the Pt（111） surface is also analyzed.展开更多
The pursuit of sustainable and environmentally benign synthetic methods continues to challenge organic chemists. Herein, we introduce a magnetoredox system for tri- and difluoromethylation of isocyanides and N-arylacr...The pursuit of sustainable and environmentally benign synthetic methods continues to challenge organic chemists. Herein, we introduce a magnetoredox system for tri- and difluoromethylation of isocyanides and N-arylacrylamides using a rotating magnetic field and steel rods. This magnetoredox approach enables facile synthesis of functionalized phenanthridines and oxindoles without the need for catalysts and additives under mild conditions. Such a system potentially represents an attractive strategy for selective formation of bonds through multifaceted regulation of magnetic intensity, rotating frequency, and rod size.展开更多
Comprehensive Summary Herein,a[1,2]-phospha-Brook rearrangement-initiated palladium-catalyzed cyclization reaction for base-controlled selective synthesis of 2H-isoindole-1-carboxamide and 2H-isoindole-1-carbonitrile ...Comprehensive Summary Herein,a[1,2]-phospha-Brook rearrangement-initiated palladium-catalyzed cyclization reaction for base-controlled selective synthesis of 2H-isoindole-1-carboxamide and 2H-isoindole-1-carbonitrile derivatives has been described.This strategy features double isocyanide insertion,efficient bond combinations,simple operation and reaction conditions.Mechanistic studies show that the[1,2]-phospha-Brook rearrangement is the key step in this reaction.This protocol offers a novel and concise strategy for the synthesis of 2H-isoindole derivatives.展开更多
Herein,it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides,simultaneously as initiators for the formation of alkyl and pho...Herein,it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides,simultaneously as initiators for the formation of alkyl and phosphoryl radicals from ethers and diarylphosphine oxides.This cascade cyclization reaction leads to diverse arylated,alkylated and phosphorylated heteroaromatic compounds.Notably,this transformation can be achieved without the aid of metals or photocatalysts,exhibiting a wide substrate applicability and operational simplicity.Mechanistic studies suggest the involvement of radical processes and electron donor-acceptor(EDA)complexes in this transformation.展开更多
A series of 3-acyl-substituted isoindolinone derivatives were synthesized in a one-pot manner via the reaction of o-bromobenzaldehydes,isocyanides,and carboxylic acids in the presence of palladium catalyst and base. T...A series of 3-acyl-substituted isoindolinone derivatives were synthesized in a one-pot manner via the reaction of o-bromobenzaldehydes,isocyanides,and carboxylic acids in the presence of palladium catalyst and base. The reaction employing easily available starting materials features simple operation and high efficiency. The mechanistic study showed that the reaction might undergo 1) Pd-catalyzed [3+2] cyclization of o-bromobenzaldehyde with isocyanide and the re-insertion of another molecule of isocyanide,2) addition of carboxylic acid to in situ formed ketenimine followed by a rearrangement relay to give 3,3-diacyl-substituted isoindolinone derivative. Further transformations of the obtained products through decarbonylation could also be realized.展开更多
Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.M...Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.展开更多
基金the National Natural Science Foundation of China(Nos.22171178, 21871174, 22071143)Innovation Program of Shanghai Municipal Education Commission (No.2019–01–07–00–09-E00008) for financial support。
文摘A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly functionalized 2-cyanopyrroles are constructed efficiently through a new formal [3 + 2] mode, demonstrating diverse reactivity and synthetic utility in organic chemistry. 2-Cyanopyrrole is converted into a nucleobase analogue of Remdesivir and 5H-pyrrolo[2,1-a]isoindole through a three-step or a two-step sequence, respectively. This protocol features broad substrate scope, operational simplicity and good functional group tolerance.
基金supported by the National Natural Science Foundation of China (No.11174215)
文摘The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp＊Mo（CO）2（=SiMe2）（SiMe3） Si-C bond were investigated extensively by using the DFT method.The effective core potentials（ECP） with a double-ζ valence basis set（LanL2DZ） were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si（ζd = 0.262）,C（ζd = 0.8） and N（ζd = 0.8）.The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.
文摘The reactive intermediate generated by the addition of alkyl isocyanides to dialkyl acetylenedicarboxylate was trapped by 6- quinolinol to produce highlyfunctionalized 4H-chromenes in fairly good yields.
文摘The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
基金supported by the Research Council of the University of Tehran as research project(No6102036/ 1/03)
文摘An efficient 1-methylimidazole-catalyzed synthesis of dialkyl 2-[（4-methylphenyl）sulfonyl]-1H-pyrrole-3,4-dicarboxylates is described.The reactive 1：1 zwitterionic intermediate formed by the addition of 1-methylimidazole to dialkyl acetylenedicarboxylates is trapped by tosylmethyl isocyanide（TOSMIC） to afford the title compounds in excellent yields.
文摘The reaction between 2-aminobenzothiazole with dialkyl acetylenedicarboxylates in the presence of isocyanides,leads to functionalized azadienes in good yields.
基金Financial support from the National Natural Science Foundation of China (Nos. 22001151, 22171168, 22101159)Taishan Scholar Program of Shandong Province and Shandong Provincial Natural Science Foundation (Nos. ZR2019QB004, ZR2020QB019) is gratefully acknowledged。
文摘A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into the C–Cu bond of organocuprate intermediate is involved for the formation of the sevenmembered azepinone ring.
文摘The addition of pyridine-2-carboxaldoxime or α-furildioxime to dialkyl acety lenedicarboxy lates under neutral conditions in the presence of alkyl isocyanides leads to ketenimines and bis（ketenimines） in good yields.
基金Financial supports from the Natural Science Foundation of Zhejiang Province(No.LY22B020010)the National Natural Science Foundation of China(Nos.21772067,21801096 and 22161043)The Youth Jinggang Scholars Program in Jiangxi Province。
文摘A palladium-catalyzed formal[2+2+1]cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein.The transformation worked well to produce a series of 7 H-acenaphtho[1,2-b]pyrrole with a broad reaction scope.Isocyanides play a dual role in the reaction.One is a C1 building block,and another is used as C1 N1 component.In the process,the[2+2+1]cyclization involves imidoylation,regioselective addition of imidoylpalladium species into alkyne,double imidoylation,and another addition of the resulting imidoylpalladium species into imine bonds.
基金financially supported by the National Natural Science Foundation of China(No.51473092)the Shanghai Rising-Star Program(No.15QA1402500)
文摘In this study,a new twisting gold（Ⅰ） isocyanide complex based on tetraphenylethene（TPE）,TPE-NC-Au.was designed and synthesized.It exhibits aggregation induced phosphorescence（AIP） characteristics,owing to the incorporation of Au moiety and conformation rigidification in the aggregated states.Moreover,the emission color of the crystalline solid of TPE-NC-Au changes from blue（454 nm） to green（500 nm） in response to mechanical grinding,due to the combined effects of conformation planarization,enhanced π…π stacking,as well as the emergence of aurophilic interactions in the ground amorphous state.Notably,the emission color can be restored upon solvent fuming,associating with the reconstruction of crystalline lattices.The AIP and switchable mechanochromism of TPE-NC-Au make it suitable for potential applications in bioimaging,sensing,and optoelectronic devices.
基金supported by the National Natural Science Foundation of China(No.21774103)the Youth Science and Technology Innovation Team of SWPU(Nos.2017CXTD05,2018CXTD05).
文摘With the exploration of novel sustainable protocol for functional polyamides'(PAs)construction as the starting point,herein,the small molecular model compound(M 1-ssBIC)was prepared firstly by manual grinding of monofunctional benzoxazine(1a)and isocyanide(1 b)via solid-state benzoxazine-isocyanide chemistry(ssBIC)to evaluate the feasibility of ssBIC.Linear PAs(P1-series polymers)were subsequently synthesized from biunctional benzoxazine(2a)and isocyanide(2b),and the influence of the loading of catalyst(octylphosphonic acid)(OPA)on the polymerization was investigated.Afterwards,two kinds of cross-linked PAs were successfully constructed via ssBIC by using trifunctional benzoxazine(3a)and cross-linked polybenzoxazine(4a)as reaction substrates,respectively,thus verifying the adaptability of ssBIC.Structural characterization indicates that amide,phenolic hydroxyl and tertiary amine substructures,with metal-complexing capability,have been successfully integrated into the obtained PAs.A type of representative PA/silver composite(P3-AgNPs)was prepared subsequently via in situ reduction treatment,and its application as recyclable reduction catalyst for organic pollutant p-nitrophenol(4-NP)was preliminarily investigated here to provide the example for possible downstream application of ssBIC.We think that this current work could provide a new pathway for the construction of functional PAs through facile and sustainable ssBIC protocol.
基金the National Natural Science Foundation of China(Nos. 21772137, 21672157, 21372174)the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 16KJA150002)+2 种基金the Ph.D. Programs Foundation of PAPDthe project of scientific and technologic infrastructure of Suzhou (No. SZS201708)Soochow University for financial support
文摘A manganese (Ⅲ)-promoted oxidative radical cascade reaction of easily accessible arylboronic acids with isocyanides to construct diimide derivatives was studied. This protocol provides a new way to synthesis of acetyl diimide derivatives. New C-C, C-N and C=O bonds were formed in one step.
基金This work was supported by NSF of Fujian Province (E0420002 and E0310029)
文摘Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr = 547.66, space group P1, a = 8.6448(1), b = 11.5772(2), c = 14.6666(4) ?, α = 88.387(2), β = 86.826(2), γ = 68.222(1)°, V = 1360.97(5) ?3, Z = 2, F(000) = 568, Dc = 1.336 g/cm3, μ = 1.582 mm-1, the final R = 0.0629 and wR = 0.1282 for 3257 observed reflections with I > 2σ(I). The phenylacetylide adopts μ-η1 and μ3-η1,η1,η2 bonding modes. The compound shows intense luminescence in the solid state.
基金Financial supports from the Natural Science Foundation of Shandong Province(Nos.ZR2019PB004 and ZR2018BB029)the Natural Science Foundation of China(Nos.21502069 and 21772067)are gratefully acknowledged。
文摘A palladium-catalyzed [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides is developed herein.The transformation worked well to produce a series of 2-amino-4-cyanofurans with high efficiency and a broad reaction scope.Based on mechanism studies,it is believed that the palladiumcatalyzed [4+1] imidoylative cycloaddition of prop-2-yn-1-ones was concerted.Treated with a ryl amine and H_2 O,the [4+1] cycloaddition of prop-2-yn-1-ones with double isocyanides provided 2-amino-4-amidylpyrroles efficiently.
基金Natural Science Foundation of Shanxi Province(No. 2009011014)
文摘The adsorption of CH3CN and CH3NC on the Pt（lll） surface at the 1/4 monolayer （ML） coverage has been car-ried out at the level of density functional theory for understanding hydrogenation processes of nitriles. The most favored ad-sorption structure for CH3 CN is the C--N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms. For CH3NC, the most stable configuration is the CH3 NC locates at the face center cubic （fcc） site with the C-atom bonded to three Pt atoms. In addition, the HCN and HNC adsorption has been computed, and the adsorption pattern is nearly similar to the CH3CN and CH3NC, respectively. The adsorbed molecules rehybridize on the surface, be-coming non-linear with a bent C-C-N or C-N-C angle. Furthermore, the binding mechanism of these molecules on the Pt（111） surface is also analyzed.
基金support by the National Natural Science Foundation of China(22101157)is gratefully acknowledgedWe are very grateful to Prof.Xiao Shen(Wuhan University,China)for helpful discussion.
文摘The pursuit of sustainable and environmentally benign synthetic methods continues to challenge organic chemists. Herein, we introduce a magnetoredox system for tri- and difluoromethylation of isocyanides and N-arylacrylamides using a rotating magnetic field and steel rods. This magnetoredox approach enables facile synthesis of functionalized phenanthridines and oxindoles without the need for catalysts and additives under mild conditions. Such a system potentially represents an attractive strategy for selective formation of bonds through multifaceted regulation of magnetic intensity, rotating frequency, and rod size.
基金financially supported by the National Natural Science Foundation of China(22071063)National Youth Talent Support Program,Guangdong Basic and Applied Basic Research Foundation(2021B1515020058 and 2024B1515040027)Guangzhou Science and Technology Projects(2024A04J6248).
文摘Comprehensive Summary Herein,a[1,2]-phospha-Brook rearrangement-initiated palladium-catalyzed cyclization reaction for base-controlled selective synthesis of 2H-isoindole-1-carboxamide and 2H-isoindole-1-carbonitrile derivatives has been described.This strategy features double isocyanide insertion,efficient bond combinations,simple operation and reaction conditions.Mechanistic studies show that the[1,2]-phospha-Brook rearrangement is the key step in this reaction.This protocol offers a novel and concise strategy for the synthesis of 2H-isoindole derivatives.
基金supported by the National Youth Talent Support Program,Guangdong Basic and Applied Basic Research Foundation(2024B1515040027)Guangzhou Science and Technology Projects(2024A04J6248).
文摘Herein,it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides,simultaneously as initiators for the formation of alkyl and phosphoryl radicals from ethers and diarylphosphine oxides.This cascade cyclization reaction leads to diverse arylated,alkylated and phosphorylated heteroaromatic compounds.Notably,this transformation can be achieved without the aid of metals or photocatalysts,exhibiting a wide substrate applicability and operational simplicity.Mechanistic studies suggest the involvement of radical processes and electron donor-acceptor(EDA)complexes in this transformation.
基金the National Natural Science Foundation of China(Nos.21772138 and 21672157)the Natural Science Foundation of Jiangsu Province(BK20221356)PAPD。
文摘A series of 3-acyl-substituted isoindolinone derivatives were synthesized in a one-pot manner via the reaction of o-bromobenzaldehydes,isocyanides,and carboxylic acids in the presence of palladium catalyst and base. The reaction employing easily available starting materials features simple operation and high efficiency. The mechanistic study showed that the reaction might undergo 1) Pd-catalyzed [3+2] cyclization of o-bromobenzaldehyde with isocyanide and the re-insertion of another molecule of isocyanide,2) addition of carboxylic acid to in situ formed ketenimine followed by a rearrangement relay to give 3,3-diacyl-substituted isoindolinone derivative. Further transformations of the obtained products through decarbonylation could also be realized.
文摘Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.
