The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging.In this study,a unique tartrate-linked dimeric samarium-antimonotungst...The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging.In this study,a unique tartrate-linked dimeric samarium-antimonotungstate[Sm_(2)(H_(2)O)_(6)(tar)(Sb_(2)W_(21)O_(72))]_(2)^(20-)(Sm_(4)tar_(2),H_(4)tar=tartaric acid)was synthesized via a one-step method at room temperature using an acetate buffer solution.The dimeric polyanion of Sm4tar2shows a centrosymmetric structure with a parallelogram-like arrangement and comprises two enantiomeric{Sm_(2)(H_(2)O)_(6)(Sb_(2)W_(21)O_(72))}moieties connected by two enantiomeric tar ligands.Sm_(4)tar_(2)demonstrates efficient catalytic activity in the three-component reaction involving 2-acylbenzoic acids,primary amines,and phosphine oxides to form 3,3-disubstituted isoindolinones.The advantages of this catalytic system include simple feedstocks,green and reusable catalyst,and operational simplicity with water as the sole by-product.This finding enables an effective molecular fragment assembly strategy for synthesizing isoindolinone drug precursor skeletons.展开更多
A H_(4)SiW_(12)O_(40)-catalyzed three-component tandem reaction of 2-acylbenzoic acids,primary amines and phosphine oxides to form 3,3-disubstituted isoindolinones was developed.By employing A H_(4)SiW_(12)O_(40)as th...A H_(4)SiW_(12)O_(40)-catalyzed three-component tandem reaction of 2-acylbenzoic acids,primary amines and phosphine oxides to form 3,3-disubstituted isoindolinones was developed.By employing A H_(4)SiW_(12)O_(40)as the catalyst and dimethyl carbonate(DMC)as the solvent,a diverse range of 2-acylbenzoic acid derivatives and primary amines worked well to give the C3-phosphinoyl-functionalized 3,3-disubstituted isoindolinones with the yield range of 61%-87%.Advantages of this transformation include green catalyst and solvent,available starting materials,broad substrate scope,high efficiency and operational simplicity with water as the sole by-product.The strategy achieved an efficient and green molecular fragment assembly to access isoindolinones,which would provide opportunities for the synthesis of potential biologically active molecules in a green manner.展开更多
A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step econ...A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step economy,mild reaction conditions,and good functional group tolerance,facilitating access to a wide range of highly-valuable functionalized isoindolinones with high level of yields(up to 99%yield).展开更多
The isoindolinone and biaryl scaffolds are prevalent in natural products and drug molecules,which have showed broad and interesting biological activities.The efficient construction of such hybridized molecules and bio...The isoindolinone and biaryl scaffolds are prevalent in natural products and drug molecules,which have showed broad and interesting biological activities.The efficient construction of such hybridized molecules and biological evaluation are of great interest to medicinal chemistry community.In this communication,we report an efficient BrΦnsted acid-promoted C(sp^3)-H functionalization approach that enables the rapid construction of biologically important isoindolinone/[1,2,4]triazolo[1,5-a]pyrimidine hybrids from 5-methyl-7-(2,4,6-trimethoxyphenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,2-formylbenzoic acid and various anilines.The title compounds were generated in high to excellent yields(up to 96%)regardless of the electronic nature and steric effects of the substituents.In this reaction,an isoindolinone scaffold,one C-C single bond,and two C-N bonds were formed simultaneously with high atom economy.In this work,we have envisioned that the methyl group linked to the electron-deficient Nheterocycles could be used as a new synthetic handle for late-state diversification and may have broad applications in the field of organic and medicinal chemistry.Besides,the title compounds have exhibited promising activity against the SKP2-CKS1 interaction.展开更多
A mild and efficient oxidative synthesis of isoindolinones has been realized by Rh(III)‐catalyzed C?H activation of benzamides and[4+1]coupling with propargyl alcohols.This coupling system proceeds with broad substra...A mild and efficient oxidative synthesis of isoindolinones has been realized by Rh(III)‐catalyzed C?H activation of benzamides and[4+1]coupling with propargyl alcohols.This coupling system proceeds with broad substrate scope and mild conditions and provides a new approach to access the useful skeleton ofγ‐lactams with a stereogenic center.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
Under photocatalytic reductive conditions,trifluoromethyl radical addition onto an ynamide followed by cyclization on a benzoyl moiety produces diverse isoindolinone platforms with good yields.The selectivity of the r...Under photocatalytic reductive conditions,trifluoromethyl radical addition onto an ynamide followed by cyclization on a benzoyl moiety produces diverse isoindolinone platforms with good yields.The selectivity of the radical cyclization,N-benzoyl vs.N-benzyl as radical acceptor and the E/Z ratio of isomers have been rationalized by modeling.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22301033)Jiangxi Provincial Natural Science Foundation(No.20232ACB213005 and 20212BAB213001)。
文摘The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging.In this study,a unique tartrate-linked dimeric samarium-antimonotungstate[Sm_(2)(H_(2)O)_(6)(tar)(Sb_(2)W_(21)O_(72))]_(2)^(20-)(Sm_(4)tar_(2),H_(4)tar=tartaric acid)was synthesized via a one-step method at room temperature using an acetate buffer solution.The dimeric polyanion of Sm4tar2shows a centrosymmetric structure with a parallelogram-like arrangement and comprises two enantiomeric{Sm_(2)(H_(2)O)_(6)(Sb_(2)W_(21)O_(72))}moieties connected by two enantiomeric tar ligands.Sm_(4)tar_(2)demonstrates efficient catalytic activity in the three-component reaction involving 2-acylbenzoic acids,primary amines,and phosphine oxides to form 3,3-disubstituted isoindolinones.The advantages of this catalytic system include simple feedstocks,green and reusable catalyst,and operational simplicity with water as the sole by-product.This finding enables an effective molecular fragment assembly strategy for synthesizing isoindolinone drug precursor skeletons.
基金the National Natural Science Foundation of China(No.22001034)Jiangxi Provincial Natural Science Foundation(No.20212BAB213001).
文摘A H_(4)SiW_(12)O_(40)-catalyzed three-component tandem reaction of 2-acylbenzoic acids,primary amines and phosphine oxides to form 3,3-disubstituted isoindolinones was developed.By employing A H_(4)SiW_(12)O_(40)as the catalyst and dimethyl carbonate(DMC)as the solvent,a diverse range of 2-acylbenzoic acid derivatives and primary amines worked well to give the C3-phosphinoyl-functionalized 3,3-disubstituted isoindolinones with the yield range of 61%-87%.Advantages of this transformation include green catalyst and solvent,available starting materials,broad substrate scope,high efficiency and operational simplicity with water as the sole by-product.The strategy achieved an efficient and green molecular fragment assembly to access isoindolinones,which would provide opportunities for the synthesis of potential biologically active molecules in a green manner.
文摘A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step economy,mild reaction conditions,and good functional group tolerance,facilitating access to a wide range of highly-valuable functionalized isoindolinones with high level of yields(up to 99%yield).
基金supported by the National Natural Science Foundation of China(Nos.81773562 and 81703326)China Postdoctoral Science Foundation(Nos.2018M630840 and 2019T120641)Scientific Program of Henan Province(No.182102310123)。
文摘The isoindolinone and biaryl scaffolds are prevalent in natural products and drug molecules,which have showed broad and interesting biological activities.The efficient construction of such hybridized molecules and biological evaluation are of great interest to medicinal chemistry community.In this communication,we report an efficient BrΦnsted acid-promoted C(sp^3)-H functionalization approach that enables the rapid construction of biologically important isoindolinone/[1,2,4]triazolo[1,5-a]pyrimidine hybrids from 5-methyl-7-(2,4,6-trimethoxyphenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,2-formylbenzoic acid and various anilines.The title compounds were generated in high to excellent yields(up to 96%)regardless of the electronic nature and steric effects of the substituents.In this reaction,an isoindolinone scaffold,one C-C single bond,and two C-N bonds were formed simultaneously with high atom economy.In this work,we have envisioned that the methyl group linked to the electron-deficient Nheterocycles could be used as a new synthetic handle for late-state diversification and may have broad applications in the field of organic and medicinal chemistry.Besides,the title compounds have exhibited promising activity against the SKP2-CKS1 interaction.
基金supported by the Dalian Institute of Chemical Physics,Chinese Academy of Sciencesthe National Natural Science Foundation of China (21525208,21472186)~~
文摘A mild and efficient oxidative synthesis of isoindolinones has been realized by Rh(III)‐catalyzed C?H activation of benzamides and[4+1]coupling with propargyl alcohols.This coupling system proceeds with broad substrate scope and mild conditions and provides a new approach to access the useful skeleton ofγ‐lactams with a stereogenic center.
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Under photocatalytic reductive conditions,trifluoromethyl radical addition onto an ynamide followed by cyclization on a benzoyl moiety produces diverse isoindolinone platforms with good yields.The selectivity of the radical cyclization,N-benzoyl vs.N-benzyl as radical acceptor and the E/Z ratio of isomers have been rationalized by modeling.
