Phenanthridine is a key structural motif in numerous natural products and biologically active compounds,making it an attractive target for pharmaceuticals and advanced materials.Recently,visible-light-induced cyclizat...Phenanthridine is a key structural motif in numerous natural products and biologically active compounds,making it an attractive target for pharmaceuticals and advanced materials.Recently,visible-light-induced cyclization through radical process has emerged as a powerful and sustainable strategy for building such a core under mild and environmentally friendly conditions,paving the way for new applications in synthetic and medicinal chemistry.This review highlights recent progress in the photochemical synthesis of phenanthridines,mainly focusing on various radical acceptors,including 2-isocyanobiaryls,cyanides,vinyl azides and vinyl benzotriazoles.展开更多
Comprehensive Summary The skeletal remodeling of nitro-biphenyl indoles has been achieved via the cleavage of C_(2)-N_(1) bond of and redistribution of the C_(2)atom.A diverse range of phenanthridines and phenanthridi...Comprehensive Summary The skeletal remodeling of nitro-biphenyl indoles has been achieved via the cleavage of C_(2)-N_(1) bond of and redistribution of the C_(2)atom.A diverse range of phenanthridines and phenanthridine N-oxides were switchably synthesized through fine-tuning the amount of HCl and reaction atmosphere.The scale-up synthesis and late-stage modification of the resulting products expand the application potential of this methodology.Furthermore,DFT calculations indicate that the ring-opening of indole necessitates the assistance of EtOH.This work establishes an attractive platform for the remodeling and conversion of N-heterocyclic frameworks.展开更多
The asymmetric hydrogenation of N-heteroarenes provides an efficient method for the synthesis of optically active cyclic secondary amines.In this paper,we described an asymmetric hydrogenation of phenanthridines using...The asymmetric hydrogenation of N-heteroarenes provides an efficient method for the synthesis of optically active cyclic secondary amines.In this paper,we described an asymmetric hydrogenation of phenanthridines using a chiral mono-alkene-derived borane.A variety of dihydrophenanthridines were furnished in high yields with up to 93%ee.The current catalytic system was very sensitive for the steric hindrance of phenanthridines.Bulky substituents at one phenyl group of phenanthridines were required to obtain the high enantioselectivity.But large substituents on the carbon of the C=N bonds would diminish the reactivity sharply.展开更多
A facile, one-pot synthesis of new phenanthridine derivatives by a three-component reaction between phenantridine, dialkyl acetylenedicarboxylates（DAADs）, and aromatic aldehydes is described. The reaction is charact...A facile, one-pot synthesis of new phenanthridine derivatives by a three-component reaction between phenantridine, dialkyl acetylenedicarboxylates（DAADs）, and aromatic aldehydes is described. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups.展开更多
A simple and efficient radical coupling of 2-isocyanobiphenyl with ethers was developed, providing a variety of 6-alkylated phenanthridines. Both cyclic and acyclic ethers are suitable substrates for this transformati...A simple and efficient radical coupling of 2-isocyanobiphenyl with ethers was developed, providing a variety of 6-alkylated phenanthridines. Both cyclic and acyclic ethers are suitable substrates for this transformation, which comprised the functional- ization of two C-H bonds： the sp3 C-H of ether and sp2 C-H of phenyl group. The kinetic isotope effect （KIE） revealed that the cleavage of sp3 C-H bond would be involved in the rate-determining step.展开更多
Here,we describe a general and modular strategy for the rapid assembly of benzo[c]phenanthridine(BCP)derivatives using homogeneous gold catalysis.Notably,in contrast to traditional methods based on the specially prefo...Here,we describe a general and modular strategy for the rapid assembly of benzo[c]phenanthridine(BCP)derivatives using homogeneous gold catalysis.Notably,in contrast to traditional methods based on the specially preformed substrates that have an inherent preference for the formation of this class of compounds with limited flexibility,this protocol is achieved via a selectively intramolecular cascade of a diazo-tethered alkyne and subsequently an intermolecular cyclization with a nitrile to facilitate the successive C–N and C–C bonds formation.This methodology uses readily available nitriles as the nitrogen source to deliver the products in good yield with excellent functional group compatibility.A preliminary anti-tumor activity study of these generated products exhibits high anticancer potency against five tumor cell lines,including He La,Mel624,SW-480,8505C,LAN-1.Besides,we report a catalyst-controlled intermolecular cycloaddition/intramolecular insertion of the substrate with a fulvene to provide fused polycarbocycles containing a seven-membered ring.展开更多
The target compound Ⅳ (C_(20)H_(21)N) was synthesized through four-step reactions and structurally determined by single-crystal X-ray diffraction.The crystal of compound Ⅳ is in the orthorhombic system,space group F...The target compound Ⅳ (C_(20)H_(21)N) was synthesized through four-step reactions and structurally determined by single-crystal X-ray diffraction.The crystal of compound Ⅳ is in the orthorhombic system,space group Fdd2 with a=41.178(19),b=30.389(8),c=4.8182(17)Å,β=90°,C_(20)H_(21)N,M_(r)=275.38,D_(c)=1.213g/cm^(3),V=6029(4)Å^(3),Z=16,F(000)=2368,μ(Mo Ka)=0.527 mm^(-1),T=240(2) K,2200 independent reflections with 1233 observed ones (I>2σ(I)),R=0.1285 and w R=0.2589 with GOF=1.050 (R=0.2058 and w R=0.3055for all data).A one-dimensional interaction model of the title compound was formed by one kind of π-π interactions between the two phenyl rings of the adjacent molecules at upper and lower levels.The inhibition to the strand transfer process of HIV-1 integrase of the target compound was also evaluated.展开更多
A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide(NHPI esters)for the construction of phenanthridine derivatives has been...A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide(NHPI esters)for the construction of phenanthridine derivatives has been developed.This approach utilizes lithium iodide(LiI)and triphenylphosphine(PPh_(3))as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor-acceptor(EDA)complex.A series of primary,secondary,and tertiary alkyl-substituted phenanthridines are prepared in up to 82%yield without transition-metal catalysts,chemical oxidants,or metal-/organic dye-based photocatalysts.展开更多
基金financially supported by the National Natural Science Foundation of China(No.21602046)the Zhongjing Youth Talent Project from Henan University of Chinese Medicine(No.03104150-2024-1-52)the Foundation for University Key Teachers from the Education Department of Henan Province(No.2020GGJS107)。
文摘Phenanthridine is a key structural motif in numerous natural products and biologically active compounds,making it an attractive target for pharmaceuticals and advanced materials.Recently,visible-light-induced cyclization through radical process has emerged as a powerful and sustainable strategy for building such a core under mild and environmentally friendly conditions,paving the way for new applications in synthetic and medicinal chemistry.This review highlights recent progress in the photochemical synthesis of phenanthridines,mainly focusing on various radical acceptors,including 2-isocyanobiaryls,cyanides,vinyl azides and vinyl benzotriazoles.
基金support was from the National Natural Science Foundation of China(No.22301071)Natural Science Foundation of Hubei Province(Nos.2023AFB459,2023AFB477)+2 种基金the Hubei Key Laboratory of Pollutant Analysis&Reuse Technology(No.PA220204)Initial Research Fund Project of North Sichuan Medical College(No.CBY21-QD06)the Sichuan Science and Technology Program(No.2023NSFSC1070).
文摘Comprehensive Summary The skeletal remodeling of nitro-biphenyl indoles has been achieved via the cleavage of C_(2)-N_(1) bond of and redistribution of the C_(2)atom.A diverse range of phenanthridines and phenanthridine N-oxides were switchably synthesized through fine-tuning the amount of HCl and reaction atmosphere.The scale-up synthesis and late-stage modification of the resulting products expand the application potential of this methodology.Furthermore,DFT calculations indicate that the ring-opening of indole necessitates the assistance of EtOH.This work establishes an attractive platform for the remodeling and conversion of N-heterocyclic frameworks.
基金financial support from the National Natural Science Foundation of China(21825108 and 22331011).
文摘The asymmetric hydrogenation of N-heteroarenes provides an efficient method for the synthesis of optically active cyclic secondary amines.In this paper,we described an asymmetric hydrogenation of phenanthridines using a chiral mono-alkene-derived borane.A variety of dihydrophenanthridines were furnished in high yields with up to 93%ee.The current catalytic system was very sensitive for the steric hindrance of phenanthridines.Bulky substituents at one phenyl group of phenanthridines were required to obtain the high enantioselectivity.But large substituents on the carbon of the C=N bonds would diminish the reactivity sharply.
文摘A facile, one-pot synthesis of new phenanthridine derivatives by a three-component reaction between phenantridine, dialkyl acetylenedicarboxylates（DAADs）, and aromatic aldehydes is described. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups.
基金This work was supported by the National Natural Science Foundation of China(21172106,21074054 and 21372114)the National Basic Research Program of China(2010CB923303)+1 种基金the Research FundJbr the Doctoral Program of Higher Education of China(20120091110010)PAN ChangDuo is thankful the support of the Natural Science Foundation of China(21272178).
文摘A simple and efficient radical coupling of 2-isocyanobiphenyl with ethers was developed, providing a variety of 6-alkylated phenanthridines. Both cyclic and acyclic ethers are suitable substrates for this transformation, which comprised the functional- ization of two C-H bonds： the sp3 C-H of ether and sp2 C-H of phenyl group. The kinetic isotope effect （KIE） revealed that the cleavage of sp3 C-H bond would be involved in the rate-determining step.
文摘Here,we describe a general and modular strategy for the rapid assembly of benzo[c]phenanthridine(BCP)derivatives using homogeneous gold catalysis.Notably,in contrast to traditional methods based on the specially preformed substrates that have an inherent preference for the formation of this class of compounds with limited flexibility,this protocol is achieved via a selectively intramolecular cascade of a diazo-tethered alkyne and subsequently an intermolecular cyclization with a nitrile to facilitate the successive C–N and C–C bonds formation.This methodology uses readily available nitriles as the nitrogen source to deliver the products in good yield with excellent functional group compatibility.A preliminary anti-tumor activity study of these generated products exhibits high anticancer potency against five tumor cell lines,including He La,Mel624,SW-480,8505C,LAN-1.Besides,we report a catalyst-controlled intermolecular cycloaddition/intramolecular insertion of the substrate with a fulvene to provide fused polycarbocycles containing a seven-membered ring.
基金supported by the Natural Science Research Projects in Colleges and Universities of Anhui Province(No.KJ2019A0116)National Training Programs of Innovation and Entrepreneurship for Undergraduates(No.202010361076)Jiangxi Education Hall Science and Technology Foundation(GJJ160998)。
文摘The target compound Ⅳ (C_(20)H_(21)N) was synthesized through four-step reactions and structurally determined by single-crystal X-ray diffraction.The crystal of compound Ⅳ is in the orthorhombic system,space group Fdd2 with a=41.178(19),b=30.389(8),c=4.8182(17)Å,β=90°,C_(20)H_(21)N,M_(r)=275.38,D_(c)=1.213g/cm^(3),V=6029(4)Å^(3),Z=16,F(000)=2368,μ(Mo Ka)=0.527 mm^(-1),T=240(2) K,2200 independent reflections with 1233 observed ones (I>2σ(I)),R=0.1285 and w R=0.2589 with GOF=1.050 (R=0.2058 and w R=0.3055for all data).A one-dimensional interaction model of the title compound was formed by one kind of π-π interactions between the two phenyl rings of the adjacent molecules at upper and lower levels.The inhibition to the strand transfer process of HIV-1 integrase of the target compound was also evaluated.
基金supported by the National Natural Science Foundation of China(22078084)the Scientific Research Fund of Hunan Provincial Education Department(22B0674)the Science and Natural Science Foundation of Hunan Province(Nos.2023J30273 and 2023J40301).
文摘A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide(NHPI esters)for the construction of phenanthridine derivatives has been developed.This approach utilizes lithium iodide(LiI)and triphenylphosphine(PPh_(3))as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor-acceptor(EDA)complex.A series of primary,secondary,and tertiary alkyl-substituted phenanthridines are prepared in up to 82%yield without transition-metal catalysts,chemical oxidants,or metal-/organic dye-based photocatalysts.
