Me OTf-catalyzed formal[4+2]annulation of styrene oxides with alkynes to afford polysubstituted naphthalenes has been realized,which undergoes sequential electrophilic cyclization/ring expansion.A range of substrates ...Me OTf-catalyzed formal[4+2]annulation of styrene oxides with alkynes to afford polysubstituted naphthalenes has been realized,which undergoes sequential electrophilic cyclization/ring expansion.A range of substrates were tolerated in the formation of naphthalene derivatives with high regioselectivity in satisfactory yields.The reaction could also be carried out on gram scale.展开更多
The seleno substituted aromatic compounds were prepared via the Diels-Alder reaction of seleno substituted 3-sulfolenes with dimethyl acetylenedicarboxylate followed by DDQ dehydrogenation.
A tandem one-pot synthesis of polysubstituted 1,3-thiazines has been developed by reacting with cyanoacetamide and isothiocyanate derivatives to give rise to 2-cyano-3-mercaptoacrylamides, which are trapped in situ by...A tandem one-pot synthesis of polysubstituted 1,3-thiazines has been developed by reacting with cyanoacetamide and isothiocyanate derivatives to give rise to 2-cyano-3-mercaptoacrylamides, which are trapped in situ by various aldehydes or diversely substituted ketones through intermolecular cyclization, providing polysubstituted 1,3-thiazine derivatives in short reaction times with good to excellent yields. The salient features of this novel protocol are operational simplicity, accessing the desired products from the readily available starting materials and easy of product isolation and may find wide spread applications in medicinal chemistry.展开更多
A versatile heteropoly acid(H_(3)PMo_(12)O_(40))-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes.Furthermore,the catalytic system was also suitab...A versatile heteropoly acid(H_(3)PMo_(12)O_(40))-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes.Furthermore,the catalytic system was also suitable for the reaction of diarylmethanols and diols/aldehydes.The application of such an earthabundant,readily accessible,and nontoxic catalyst provides a green approach for the construction of polyaryl-substituted aldehydes.展开更多
Intermolecular addition-cyclization of 1, 3-dicarbonyl compounds with arylbromo- allenes in K2CO3 mediated condition afforded 2, 3, 4-trisubstituted furans in good yield.
A kind of polysubstituted benzene, 3-amino-5,6-dimethyl-2-nitrobiphenyl-4-carbonitrile(C15H13N3O2), was synthesized and its crystal structure was determined. The molecule is composed of two phenyl moieties, two methyl...A kind of polysubstituted benzene, 3-amino-5,6-dimethyl-2-nitrobiphenyl-4-carbonitrile(C15H13N3O2), was synthesized and its crystal structure was determined. The molecule is composed of two phenyl moieties, two methyl groups, a cyano group, an amino group and a nitro group. The methyl groups, cyano group and amino group are nearly coplanar with the connected benzene ring. Because of the large volume, the nitro group and the connected benzene ring are twisted. The dihedral angle between the two benzene rings is 83.51°. In the crystal, molecules are linked by N—H···N and C—H···O hydrogen bonds.展开更多
Poly-substituted olefins,one of the most important aggregation-induced emission luminogens(AIEgens),have garnered significant attention due to their various applications in chemical-and bio-sensing,bio-imaging,and opt...Poly-substituted olefins,one of the most important aggregation-induced emission luminogens(AIEgens),have garnered significant attention due to their various applications in chemical-and bio-sensing,bio-imaging,and opto-electronics.However,the synthetic methods for these olefins remain limited,impeding the progress of AIEgens.This study introduces an unprecedented cross-coupling reaction between aryl sulfonium triflates and tosylhydrazones from naturally abundant thioethers and ketones.The generality of this method is exemplified by the facile synthesis of over forty poly-substituted olefins.Importantly,the luminescent properties of these AIEgens(e.g.,quantum yield and emission color)can be easily tuned by adjusting the substituents of the electrophile and nucleophile substrates,exhibiting excellent performance in bio-imaging.Notably,the mechanistic studies reveal the critical role ofβ-H elimination in the formation of the double bond.This contribution provides an efficient method to synthesize poly-substituted olefins,pushing forward the development of AIEgens.展开更多
The acyclic precursors, methyl 3-perfluoroalkyl-4-carbethoxy-5-methoxy-6-(triphenylphosphoranylidene)hexa- 2,4-dienoates (4) were obtained via the addition reaction of ethyl 3-methoxy-4-(triphenylphosphoranylidene)but...The acyclic precursors, methyl 3-perfluoroalkyl-4-carbethoxy-5-methoxy-6-(triphenylphosphoranylidene)hexa- 2,4-dienoates (4) were obtained via the addition reaction of ethyl 3-methoxy-4-(triphenylphosphoranylidene)but-2- enoate (2) with equally molar methyl 2-perfluoroalkynoates (3). Ethyl 2,4-dimethoxy-6-perfluoroalkylbenzoates (5) were synthesized in high yield via an intramolecular elimination of Ph3PO of 4 by heating in anhydrous benzene in a sealed tube. The structure of these compounds was confirmed by IR, 1H, 13C, 2D C-H cosy NMR and mass spectra and elemental analyses. The possible reaction mechanisms were also proposed.展开更多
The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroalkynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (...The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroalkynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0 degrees C. Intramolecular elimination of Ph(3)PO took place when compound 5 was heated in aqueous methanol at 115-120 degrees C in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, H-1 NMR, F-19 NMR and C-13 NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.展开更多
基金the National Key Research and Development Program of China(No.2016YFB0401400)the National Natural Science Foundation of China(Nos.21871163 and 22071134)。
文摘Me OTf-catalyzed formal[4+2]annulation of styrene oxides with alkynes to afford polysubstituted naphthalenes has been realized,which undergoes sequential electrophilic cyclization/ring expansion.A range of substrates were tolerated in the formation of naphthalene derivatives with high regioselectivity in satisfactory yields.The reaction could also be carried out on gram scale.
文摘The seleno substituted aromatic compounds were prepared via the Diels-Alder reaction of seleno substituted 3-sulfolenes with dimethyl acetylenedicarboxylate followed by DDQ dehydrogenation.
基金Project supported by the National Natural Science Foundationof China （Nos. 21072163, 21002083 and 21110102002）, the Science Foundation in Interdisciplinary Major Research Project of Xuzhou Normal University （No. 09XKXK01）, the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Doctoral Research Foundation of Xuzhou Normal University （No. 10XLR20）.
文摘A tandem one-pot synthesis of polysubstituted 1,3-thiazines has been developed by reacting with cyanoacetamide and isothiocyanate derivatives to give rise to 2-cyano-3-mercaptoacrylamides, which are trapped in situ by various aldehydes or diversely substituted ketones through intermolecular cyclization, providing polysubstituted 1,3-thiazine derivatives in short reaction times with good to excellent yields. The salient features of this novel protocol are operational simplicity, accessing the desired products from the readily available starting materials and easy of product isolation and may find wide spread applications in medicinal chemistry.
基金the financial support from the National Natural Science Foundation of China(Nos.21871026,21971224)Research Found of East China University of Technology(Nos.DHBK2019265,DHBK2019267,DHBK2019264)。
文摘A versatile heteropoly acid(H_(3)PMo_(12)O_(40))-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes.Furthermore,the catalytic system was also suitable for the reaction of diarylmethanols and diols/aldehydes.The application of such an earthabundant,readily accessible,and nontoxic catalyst provides a green approach for the construction of polyaryl-substituted aldehydes.
基金We are grateful to the National Natural Science Foundation of China(No.20472072,20332060).
文摘Intermolecular addition-cyclization of 1, 3-dicarbonyl compounds with arylbromo- allenes in K2CO3 mediated condition afforded 2, 3, 4-trisubstituted furans in good yield.
文摘A kind of polysubstituted benzene, 3-amino-5,6-dimethyl-2-nitrobiphenyl-4-carbonitrile(C15H13N3O2), was synthesized and its crystal structure was determined. The molecule is composed of two phenyl moieties, two methyl groups, a cyano group, an amino group and a nitro group. The methyl groups, cyano group and amino group are nearly coplanar with the connected benzene ring. Because of the large volume, the nitro group and the connected benzene ring are twisted. The dihedral angle between the two benzene rings is 83.51°. In the crystal, molecules are linked by N—H···N and C—H···O hydrogen bonds.
基金support from the National Natural Science Foundation of China(51925306,52120105006,52222309,52173187,and 52303221)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB 0520103)+3 种基金Beijing Natural Science Foundation(Z210017)the Science and Technology Innovation Commission of Shenzhen(JCYJ20220530150604009)Project of International Cooperation of Chinese Academy of Sciences(124GJHZ2023079MI)Xiaomi Young Talents Program,and Fundamental Research Funds for the Central University.
文摘Poly-substituted olefins,one of the most important aggregation-induced emission luminogens(AIEgens),have garnered significant attention due to their various applications in chemical-and bio-sensing,bio-imaging,and opto-electronics.However,the synthetic methods for these olefins remain limited,impeding the progress of AIEgens.This study introduces an unprecedented cross-coupling reaction between aryl sulfonium triflates and tosylhydrazones from naturally abundant thioethers and ketones.The generality of this method is exemplified by the facile synthesis of over forty poly-substituted olefins.Importantly,the luminescent properties of these AIEgens(e.g.,quantum yield and emission color)can be easily tuned by adjusting the substituents of the electrophile and nucleophile substrates,exhibiting excellent performance in bio-imaging.Notably,the mechanistic studies reveal the critical role ofβ-H elimination in the formation of the double bond.This contribution provides an efficient method to synthesize poly-substituted olefins,pushing forward the development of AIEgens.
基金Project supported by the National Natural Science Foundation of China (No. 20172037).
文摘The acyclic precursors, methyl 3-perfluoroalkyl-4-carbethoxy-5-methoxy-6-(triphenylphosphoranylidene)hexa- 2,4-dienoates (4) were obtained via the addition reaction of ethyl 3-methoxy-4-(triphenylphosphoranylidene)but-2- enoate (2) with equally molar methyl 2-perfluoroalkynoates (3). Ethyl 2,4-dimethoxy-6-perfluoroalkylbenzoates (5) were synthesized in high yield via an intramolecular elimination of Ph3PO of 4 by heating in anhydrous benzene in a sealed tube. The structure of these compounds was confirmed by IR, 1H, 13C, 2D C-H cosy NMR and mass spectra and elemental analyses. The possible reaction mechanisms were also proposed.
基金Project supported by the National Natural Science Foundation of China.
文摘The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroalkynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0 degrees C. Intramolecular elimination of Ph(3)PO took place when compound 5 was heated in aqueous methanol at 115-120 degrees C in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, H-1 NMR, F-19 NMR and C-13 NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.
