The first cyclization/decarboxylation reaction of isatins with acyl chlorides promoted by 4-dimethylaminopyridine(DMAP)was described and a series of desired 3-alkenyl-oxindoles were obtained in good yields(up to 80%)a...The first cyclization/decarboxylation reaction of isatins with acyl chlorides promoted by 4-dimethylaminopyridine(DMAP)was described and a series of desired 3-alkenyl-oxindoles were obtained in good yields(up to 80%)and E/Z selectivities(up to 6.4/1).This protocol provided a new and feasible access to 3-alkenyl-oxindoles.展开更多
Difluoromethyl compounds are widely found in natural products,bioactive molecule and pharmaceuticals.A visible-light induced difluoromethylation/cyclization of 2-aryl indoles is described to construct indolo[2,1-a]iso...Difluoromethyl compounds are widely found in natural products,bioactive molecule and pharmaceuticals.A visible-light induced difluoromethylation/cyclization of 2-aryl indoles is described to construct indolo[2,1-a]isoquinolin-6(5H)-one derivatives using the inexpensive and easy-to-handle HCF_(2)SO_(2)Na as an HCF2 sources.Diverse difluoromethylated indolo[2,1-a]isoquinolines were readily obtained in moderate to good yields.Mechanistic studies demonstrate that the reaction may involve a radical process.展开更多
Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the con...Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1-α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant.The present protocol exhibits good functional group tolerance,and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields.Radical trapping experiments indicated that the reaction may involve a radical process.展开更多
The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-h...The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-helicenes:one with a single heptagon(5)and another with two heptagons(6),achieved through controlled oxidative cyclization of a triple oxa-helicene(4).UV-vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6,attributed toπ-system extension and greater structural relaxation in the excited state.5 and 6 exhibited fluorescence quantum yields 2-3times higher than 4.Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4,due to planarization effects induced by heptagon incorporation.The chiroptical properties were also investigated,revealing reduced optical dissymmetry factors after heptagon embedding.展开更多
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the...The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the use of chiral Br?nsted acids as catalysts.Here,we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction,allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities.Thus,this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement,but also constitutes the first example of asymmetric formal monocarbon insertion into C-O bond of ester.Moreover,theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.展开更多
Asperfilasin A(1),featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core,represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes.The enantioselective total synthesis was efficientl...Asperfilasin A(1),featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core,represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes.The enantioselective total synthesis was efficiently accomplished from the key intermediate(S)-6 with three contiguous stereocenters in 5 steps and the synthetic 1 induced G2/M-phase cell cycle arrest of HT29 cells and apoptosis of HL60 and NB4 cells by activation of caspase-3 and degradation of PARP.(S)-6,bearing three contiguous chiral centers,was efficiently constructed by a novel Nazarov cyclization reaction containing basic nitrogen,which was less developed,primarily due to the incompatibility of basic nitrogen under acidic reaction conditions.This reaction allows a wide range of pentadienone substrates containing basic nitrogen to undergo Nazarov cyclization in a single regioselective and diastereoselective manner and is capable of generating three stereocenters simultaneously.Furthermore,the mechanism of the Nazarov cyclization and the origin of the regio-and diastereoselectivity were elucidated by DFT calculations and deuteration experiments,providing valuable insights into the reaction and serving as a guide for future applications involving substrates containing basic nitrogen.展开更多
A general method was described to synthesize a highly hydrophobic cyclic peptide,cyclo[LWLWLWLWLQ]where underlines indicate D-configuration of the amino acid,by a two-step solid-phase/solution synthesis strategy.The l...A general method was described to synthesize a highly hydrophobic cyclic peptide,cyclo[LWLWLWLWLQ]where underlines indicate D-configuration of the amino acid,by a two-step solid-phase/solution synthesis strategy.The linear decapeptide was assembled by standard Boc chemistry on solid-phase and subsequently cyclized in solution with high efficiency and reproducibility. In subsequent purification by semi-preparative HPLC,50%(v/v) DMF/H_2O was employed as the solvent to overcome the difficulty of solubilization...展开更多
A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yi...A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.展开更多
Cyclopeptidomimetics are class of cyclopeptides with unnatural linkage. They usually displayed unique constrained structure, enhanced proteolytic stability, and other drug-like character; and have been widely used in ...Cyclopeptidomimetics are class of cyclopeptides with unnatural linkage. They usually displayed unique constrained structure, enhanced proteolytic stability, and other drug-like character; and have been widely used in medicinal chemistry. Therefore, development of efficient strategies for the synthesis of cyclopeptidomimetics has received many attentions. On-resin cyclization strategy is one of the effective approaches developed to overcome the competing side reaction such as oligomerization and cyclooligomers occurred in solution cyclization. This approach took advantage of the ＂pseudo-dilution＂ effect to avoid these undesired by-products and greatly simplified the downstream product purification process. This review summarized the recent on-resin peptide cyclization strategies for the synthesis of cvclooeotidomimetics.展开更多
Two three-dimensional lanthanide（Ⅲ） coordination polymers with the formula [Ln（PYDC）（NA）（H2O）]n [Ln=Gd（1）, Eu（2）, H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthe...Two three-dimensional lanthanide（Ⅲ） coordination polymers with the formula [Ln（PYDC）（NA）（H2O）]n [Ln=Gd（1）, Eu（2）, H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are isomorphous, they possess the 43.63 topology assembled by Gd^3＋/Eu^3＋ and two different multidentate carboxylate ligands Magnetic measurements show that antiferromagnetic coupling exists between adjacent Gd^3＋ ions in complex 1. The complex 2 exhibits the corresponding characteristic luminescence in the visible region under an excitation at 305 nm.展开更多
Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides....Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.展开更多
The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave field.Sodium oleate was used as the mo...The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave field.Sodium oleate was used as the model compound to study the decarboxylation of oleic acid leading to hydrocarbon formation via microwave-assisted pyrolysis technology.The pyrolysis gas,liquid,and solid products were precisely analyzed to deduce the mechanism for decarboxylation of sodium oleate.Microwave energy was able to selectively heat the carboxyl terminal of sodium oleate.During decarboxylation,the double bond in the long hydrocarbon chain formed a p-πconjugated system with the carbanion intermediate.The resulting p-πconjugated system was more stable and beneficial to the pyrolysis reaction(decarboxylation,terminal allylation,isomerization,and aromatization).The physical properties of pyrolysis liquid were generally similar to those of diesel fuel,thereby demonstrating the possible use of microwaves for controlling the decarboxylation of sodium oleate in order to manufacture renewable hydrocarbon fuels.展开更多
1-[1-（Benzyloxy）-3-methylnaphthalen-4-yloxy]propan-2-one （la） took place a cyclization, debenzylation and oxidation to form 9-substitued benzo[de]chromene-7,8-dione （2a） and 5-benzyl-9-substitued benzo[de]chrome...1-[1-（Benzyloxy）-3-methylnaphthalen-4-yloxy]propan-2-one （la） took place a cyclization, debenzylation and oxidation to form 9-substitued benzo[de]chromene-7,8-dione （2a） and 5-benzyl-9-substitued benzo[de]chromene-7,8-dione （3a）. The mechanisms for these reactions were discussed.展开更多
Stereoselective functionalization at C-2 and C-3 of the gibberellin skeleton was achieved via an intramolecular free radical cyclization approach using a tethered C-19 halomethyl ester as the radical precursor.
A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol...A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol silyl ether. This reaction provides a facile access to highly enantioenriched 4- diphenylphosphinyl chroman-2-ols. It also represents a novel organocatalytic asymmetric phospha- Michael addition of α,β-unsaturated aldehydes with pentavalent P-nucleophiles.展开更多
A new and convenient visible-light-induced method has been developed for the synthesis of sulfonylated benzofurans via oxidative cyclization reaction of 1,6-enynes and arylsulfinic acids.This reaction was carried out ...A new and convenient visible-light-induced method has been developed for the synthesis of sulfonylated benzofurans via oxidative cyclization reaction of 1,6-enynes and arylsulfinic acids.This reaction was carried out under metal-free and mild conditions,in which the C-S,C-C and C=O bonds could be sequentially formed in one pot operation.展开更多
A new electrochemical strategy for trifluoromethylation/cyclization using TfNHNHBoc as a CF_(3)source was established.This approach was realized by the direct electrolysis of Tf NHNHBoc under external oxidantfree and ...A new electrochemical strategy for trifluoromethylation/cyclization using TfNHNHBoc as a CF_(3)source was established.This approach was realized by the direct electrolysis of Tf NHNHBoc under external oxidantfree and catalyst-free conditions,and afforded various trifluoromethylated oxindoles with good functional group compatibility and broad substrate scope.Preliminary mechanistic studies show that the reaction proceeds by a radical process.展开更多
An assembly of Keggin polyoxomolybdate and organic substrate （Hbipy）3[PM01204o] （1, bipy = 2,2＇- bipyridine） was synthesized and characterized by elemental analysis, infrared spectrum, and single- crystal X-ray a...An assembly of Keggin polyoxomolybdate and organic substrate （Hbipy）3[PM01204o] （1, bipy = 2,2＇- bipyridine） was synthesized and characterized by elemental analysis, infrared spectrum, and single- crystal X-ray analysis. The ligand bipy of compound 1 was generated by a decarboxylation coupling reaction of H2pdc （H2pdc = pyridine-2,6-dicarboxylic acid） in situ under hydrothermal reaction conditions and the control experiments illustrate that La（NO3）3 or Ce（NO3）3, which does not appear in the final structure, is necessary for the decarboxylation coupling reaction. Moreover, compound 1 displays strong photoluminescence property in the solid state at room temperature.展开更多
Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Be...Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Bergman cyclization in a refluxing diphenyl ether bath under vacuum to obtain conjugated polyphenylenes with the weight-average molecular weights up to 4.9 × 103 g·mol·1. The occurrence of Bergman cyclization was confirmed by 1H-NMR, 13C-NMR, and IR spectroscopic analysis. These polyphenylenes are fully soluble in common organic solvents and exhibit good thermal stability. The optical properties of the polyphenylenes were investigated by UV-Vis absorption and photoluminescence（PL） spectroscopies. A blue emission was observed for all these polyphenylenes.展开更多
Based on a mechanism analogous to the serine/threonine ligation, the aspartic acid ligation, which is facilitated by the γ-amino alcohol based ligation and oxidation, is developed and applied to the synthesis of cycl...Based on a mechanism analogous to the serine/threonine ligation, the aspartic acid ligation, which is facilitated by the γ-amino alcohol based ligation and oxidation, is developed and applied to the synthesis of cyclic peptides. The γ-hydroxyl group triggers the ring-chain tautomerization via a 6-endo-trig process,while the δ-hydroxyl group facilitates the oxidative cleavage of the vicinal diol to give carboxylic acid.展开更多
基金We are grateful for the grants from the National Natural Science Foundation of China(No.21272230)Western Light Talent Culture Project of Chinese Academy of Sciences.
文摘The first cyclization/decarboxylation reaction of isatins with acyl chlorides promoted by 4-dimethylaminopyridine(DMAP)was described and a series of desired 3-alkenyl-oxindoles were obtained in good yields(up to 80%)and E/Z selectivities(up to 6.4/1).This protocol provided a new and feasible access to 3-alkenyl-oxindoles.
文摘Difluoromethyl compounds are widely found in natural products,bioactive molecule and pharmaceuticals.A visible-light induced difluoromethylation/cyclization of 2-aryl indoles is described to construct indolo[2,1-a]isoquinolin-6(5H)-one derivatives using the inexpensive and easy-to-handle HCF_(2)SO_(2)Na as an HCF2 sources.Diverse difluoromethylated indolo[2,1-a]isoquinolines were readily obtained in moderate to good yields.Mechanistic studies demonstrate that the reaction may involve a radical process.
文摘Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1-α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant.The present protocol exhibits good functional group tolerance,and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields.Radical trapping experiments indicated that the reaction may involve a radical process.
基金financially supported by the Ministry of Science and Technology of China(No.2017YFA0204902)the National Natural Science Foundation of China(Nos.21901217,22101241)。
文摘The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-helicenes:one with a single heptagon(5)and another with two heptagons(6),achieved through controlled oxidative cyclization of a triple oxa-helicene(4).UV-vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6,attributed toπ-system extension and greater structural relaxation in the excited state.5 and 6 exhibited fluorescence quantum yields 2-3times higher than 4.Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4,due to planarization effects induced by heptagon incorporation.The chiroptical properties were also investigated,revealing reduced optical dissymmetry factors after heptagon embedding.
基金financial support from the National Natural Science Foundation of China(Nos.22125108,22101238,22331004 and 22121001)Yunnan Fundamental Research Project(No.202401CF070024)+2 种基金Natural Science Foundation of Jiangsu Province(No.BK20211059)the Project of Science and Technology of Xuzhou Government(No.KC22080)NFFTBS(No.J1310024)。
文摘The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the use of chiral Br?nsted acids as catalysts.Here,we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction,allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities.Thus,this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement,but also constitutes the first example of asymmetric formal monocarbon insertion into C-O bond of ester.Moreover,theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
基金supported by the National Natural Science Foundation of China(Nos.81725021,81903461)the National Key R&D Program of China(No.2022YFA1503200)the Natural Science Foundation of Hubei Province(No.ZRMS2023000340)。
文摘Asperfilasin A(1),featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core,represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes.The enantioselective total synthesis was efficiently accomplished from the key intermediate(S)-6 with three contiguous stereocenters in 5 steps and the synthetic 1 induced G2/M-phase cell cycle arrest of HT29 cells and apoptosis of HL60 and NB4 cells by activation of caspase-3 and degradation of PARP.(S)-6,bearing three contiguous chiral centers,was efficiently constructed by a novel Nazarov cyclization reaction containing basic nitrogen,which was less developed,primarily due to the incompatibility of basic nitrogen under acidic reaction conditions.This reaction allows a wide range of pentadienone substrates containing basic nitrogen to undergo Nazarov cyclization in a single regioselective and diastereoselective manner and is capable of generating three stereocenters simultaneously.Furthermore,the mechanism of the Nazarov cyclization and the origin of the regio-and diastereoselectivity were elucidated by DFT calculations and deuteration experiments,providing valuable insights into the reaction and serving as a guide for future applications involving substrates containing basic nitrogen.
基金supported by National Natural Science Foundation(No.30672546)Shanghai Municipal Committee of S & T(No.0652nm013)National Key Basic Research Program of China(No.2007CB935800)
文摘A general method was described to synthesize a highly hydrophobic cyclic peptide,cyclo[LWLWLWLWLQ]where underlines indicate D-configuration of the amino acid,by a two-step solid-phase/solution synthesis strategy.The linear decapeptide was assembled by standard Boc chemistry on solid-phase and subsequently cyclized in solution with high efficiency and reproducibility. In subsequent purification by semi-preparative HPLC,50%(v/v) DMF/H_2O was employed as the solvent to overcome the difficulty of solubilization...
文摘A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.
基金supported by the National Natural Science Foundation of China (No.21472070)the Project for Jiangsu Scientific and Technological Innovation Team+1 种基金Fund for Jiangsu Distinguished Professorship ProgramProject Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions,the 111 Project (No.111-2-06)
文摘Cyclopeptidomimetics are class of cyclopeptides with unnatural linkage. They usually displayed unique constrained structure, enhanced proteolytic stability, and other drug-like character; and have been widely used in medicinal chemistry. Therefore, development of efficient strategies for the synthesis of cyclopeptidomimetics has received many attentions. On-resin cyclization strategy is one of the effective approaches developed to overcome the competing side reaction such as oligomerization and cyclooligomers occurred in solution cyclization. This approach took advantage of the ＂pseudo-dilution＂ effect to avoid these undesired by-products and greatly simplified the downstream product purification process. This review summarized the recent on-resin peptide cyclization strategies for the synthesis of cvclooeotidomimetics.
基金Supported by the Education Department Science Foundation of Liaoning Province(No.2008581)the Doctor Foundation of Liaoning Province(No.20071016)+1 种基金SRF for ROCS,SEM(No.200908)Liaoning BaiQian Wan Talents Program
文摘Two three-dimensional lanthanide（Ⅲ） coordination polymers with the formula [Ln（PYDC）（NA）（H2O）]n [Ln=Gd（1）, Eu（2）, H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are isomorphous, they possess the 43.63 topology assembled by Gd^3＋/Eu^3＋ and two different multidentate carboxylate ligands Magnetic measurements show that antiferromagnetic coupling exists between adjacent Gd^3＋ ions in complex 1. The complex 2 exhibits the corresponding characteristic luminescence in the visible region under an excitation at 305 nm.
基金partial financial support from the Ministry of Science and Technology of China (No. 2016YFE0132600)Zhengzhou University
文摘Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.
基金the National Natural Science Foundation of China(No.21266022)the National High Technology Research and Development Program 863(2012AA101800-03+4 种基金2012AA02120562012AA021704)the International Cooperation of Jiangxi Province(No.20101208)the International Science & Technology Cooperation Program of China(No.2010DFB63750)the Natural Science Foundation of Jiangxi Province(No.2008GZH0047)
文摘The carboxyl terminal of sodium oleate has a stronger polarity than that of oleic acid;this terminal is more likely to be dipole polarized and ionically conductive in a microwave field.Sodium oleate was used as the model compound to study the decarboxylation of oleic acid leading to hydrocarbon formation via microwave-assisted pyrolysis technology.The pyrolysis gas,liquid,and solid products were precisely analyzed to deduce the mechanism for decarboxylation of sodium oleate.Microwave energy was able to selectively heat the carboxyl terminal of sodium oleate.During decarboxylation,the double bond in the long hydrocarbon chain formed a p-πconjugated system with the carbanion intermediate.The resulting p-πconjugated system was more stable and beneficial to the pyrolysis reaction(decarboxylation,terminal allylation,isomerization,and aromatization).The physical properties of pyrolysis liquid were generally similar to those of diesel fuel,thereby demonstrating the possible use of microwaves for controlling the decarboxylation of sodium oleate in order to manufacture renewable hydrocarbon fuels.
基金We are indebted to the National Natural Science Foundation of China （No.20272085,20472117）the Guangzhou City Science Foundation,the Guangdong Provincial Science Foundation（031594）the Scientific Research Foundation for the Returned 0verseas Chinese Scholars,and the HongKong Polytechnic University Area of Strategic Development Fund for financial support of this study.
文摘1-[1-（Benzyloxy）-3-methylnaphthalen-4-yloxy]propan-2-one （la） took place a cyclization, debenzylation and oxidation to form 9-substitued benzo[de]chromene-7,8-dione （2a） and 5-benzyl-9-substitued benzo[de]chromene-7,8-dione （3a）. The mechanisms for these reactions were discussed.
文摘Stereoselective functionalization at C-2 and C-3 of the gibberellin skeleton was achieved via an intramolecular free radical cyclization approach using a tethered C-19 halomethyl ester as the radical precursor.
基金Financial support from the National Natural Science Foundation of China(Nos. 21472096, J1103306)
文摘A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol silyl ether. This reaction provides a facile access to highly enantioenriched 4- diphenylphosphinyl chroman-2-ols. It also represents a novel organocatalytic asymmetric phospha- Michael addition of α,β-unsaturated aldehydes with pentavalent P-nucleophiles.
基金supported by the Natural Science Foundation of Shandong Province (No. ZR2018MB009)the International Cooperation Project of Qinghai Province (No. 2018-HZ-806)+1 种基金the Qinghai Key Laboratory of Tibetan Medicine Research (No. 2017-ZJ-Y11)the National Natural Science Foundation of China (No. 21302109)
文摘A new and convenient visible-light-induced method has been developed for the synthesis of sulfonylated benzofurans via oxidative cyclization reaction of 1,6-enynes and arylsulfinic acids.This reaction was carried out under metal-free and mild conditions,in which the C-S,C-C and C=O bonds could be sequentially formed in one pot operation.
基金supported by the Natural Science Foundation of Shanghai(No.20ZR1471600)the Science and Technology Commission of Shanghai Municipality(No.19DZ2271100)the Open Research Fund Program of CAS Key Laboratory of Energy Regulation Materials(No.ORFP2020–06)。
文摘A new electrochemical strategy for trifluoromethylation/cyclization using TfNHNHBoc as a CF_(3)source was established.This approach was realized by the direct electrolysis of Tf NHNHBoc under external oxidantfree and catalyst-free conditions,and afforded various trifluoromethylated oxindoles with good functional group compatibility and broad substrate scope.Preliminary mechanistic studies show that the reaction proceeds by a radical process.
基金supported by the National Natural Science Foundation of China(Nos.21173021,21231002, 21276026,20801036,51002180)the 111 Project(No. B07012)the Program of Cooperation of the Beijing Education Commission(No.20091739006)
文摘An assembly of Keggin polyoxomolybdate and organic substrate （Hbipy）3[PM01204o] （1, bipy = 2,2＇- bipyridine） was synthesized and characterized by elemental analysis, infrared spectrum, and single- crystal X-ray analysis. The ligand bipy of compound 1 was generated by a decarboxylation coupling reaction of H2pdc （H2pdc = pyridine-2,6-dicarboxylic acid） in situ under hydrothermal reaction conditions and the control experiments illustrate that La（NO3）3 or Ce（NO3）3, which does not appear in the final structure, is necessary for the decarboxylation coupling reaction. Moreover, compound 1 displays strong photoluminescence property in the solid state at room temperature.
基金financially supported by the National Natural Science Foundation of China(Nos.20874026 and 91023008)Ph.D.Programs Foundation of Ministry of Education of China(20100074110002)+1 种基金the Fundamental Research Funds for the Central Universities,Shanghai Leading Academic Discipline Project(B502)AH thanks the"Eastern Scholar Professorship"support from Shanghai local government
文摘Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Bergman cyclization in a refluxing diphenyl ether bath under vacuum to obtain conjugated polyphenylenes with the weight-average molecular weights up to 4.9 × 103 g·mol·1. The occurrence of Bergman cyclization was confirmed by 1H-NMR, 13C-NMR, and IR spectroscopic analysis. These polyphenylenes are fully soluble in common organic solvents and exhibit good thermal stability. The optical properties of the polyphenylenes were investigated by UV-Vis absorption and photoluminescence（PL） spectroscopies. A blue emission was observed for all these polyphenylenes.
基金supported by the Research Grants Council (Nos. 17309616, C6009-15G) of Hong KongThe National Science Foundation of China (Nos. 21672180, 91753101)the Area of Excellence Scheme of the University of Grants Committee of Hong Kong (No. AoE/P-705/16)
文摘Based on a mechanism analogous to the serine/threonine ligation, the aspartic acid ligation, which is facilitated by the γ-amino alcohol based ligation and oxidation, is developed and applied to the synthesis of cyclic peptides. The γ-hydroxyl group triggers the ring-chain tautomerization via a 6-endo-trig process,while the δ-hydroxyl group facilitates the oxidative cleavage of the vicinal diol to give carboxylic acid.
