Thirty-one new 10,12-disubstituted aloperine derivatives were subtly constructed through a selective oxidation on the 10-α-C-H induced by sulfonyl and a nucleophilic substitution with the stereoselectivity and scalab...Thirty-one new 10,12-disubstituted aloperine derivatives were subtly constructed through a selective oxidation on the 10-α-C-H induced by sulfonyl and a nucleophilic substitution with the stereoselectivity and scalability.Of them,compound 6b displayed a moderate anti-human coronavirus OC43(HCoV-OC43)potency and blocked the viral entry stage through a host mechanism of action.Using chemoproteomic techniques,both transmembrane serine protease 2(TMPRSS2)and scavenger receptor class B type 1(SR-B1)proteins,which act as host cofactors of viral entry,were identified to be the direct targets of 6b against HCoV-OC43.Furthermore,6b may deactivate the TMPRSS2 by inducing a change in protein conformation,rather than binding to its catalytic center,thus suppressing the viral membrane fusion.Accordingly,our study provided key scientific data for the development of aloperine derivatives into a new class of antiviral candidates against humanβ-coronavirus,including severe acute respiratory syndrome coronavirus 2(SARS-CoV-2).展开更多
Sterically congested 2,2-disubstituted indane-1,3-dione derivatives have been syn-thesized and characterized by 1H NMR,13C NMR,FT-IR and elemental analysis.The B3LYP/HF calculations for computation of IR spectra have ...Sterically congested 2,2-disubstituted indane-1,3-dione derivatives have been syn-thesized and characterized by 1H NMR,13C NMR,FT-IR and elemental analysis.The B3LYP/HF calculations for computation of IR spectra have been carried out for the title compounds at the 6-31G and 6-311＋＋G basis set levels.Predicted vibrational frequencies have been assigned and compared with the experimental FT-IR spectra and they are supported each other.展开更多
A strategy for the synthesis of 1,2-disubstituted benzimidazoles has been developed and a variety of 1,2-disubstituted benzimidazoles were obtained from imidoyl chlorides and o-haloanilines via copper（I）-catalyzed r...A strategy for the synthesis of 1,2-disubstituted benzimidazoles has been developed and a variety of 1,2-disubstituted benzimidazoles were obtained from imidoyl chlorides and o-haloanilines via copper（I）-catalyzed reaction in moderate yields.展开更多
Reaction of polymer-supported a-selenoaldehydes with Grignard reagents afforded polymer-bound B-hydroxyalkyl selenides, which treated with thionyl chloride and triethylamine leading to (E)-1, 2-disubstituted ethenes i...Reaction of polymer-supported a-selenoaldehydes with Grignard reagents afforded polymer-bound B-hydroxyalkyl selenides, which treated with thionyl chloride and triethylamine leading to (E)-1, 2-disubstituted ethenes in good yield.展开更多
Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted alde...Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted aldehydes in good to excellent isolated yields （85-95%） using water as solvent at ambient temperature. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （20--40 rain） reactions and excellent yields of products.展开更多
cis-1,2-Disubstituted cyclododecanes 2 were synthesized by sodium borohydride reduction of 2-monosubstituted cyclododecanones and their structures were confirmed by 1HNMR, ^13C NMR and elemental analysis. The higher c...cis-1,2-Disubstituted cyclododecanes 2 were synthesized by sodium borohydride reduction of 2-monosubstituted cyclododecanones and their structures were confirmed by 1HNMR, ^13C NMR and elemental analysis. The higher cis-selectivity of NaBH4 reduction of 2- monosubstituted cyclododecanones was rationalized by the mode of ＂corner position carbonyl participation＂. Crystal data for 2c： Mr = 263.21, monoclinic, space group P21/c, a = 1.11140（7）, b = 2.62590（17）, c = 0.91360（6） nm, β= 106.1840（10）°, V = 2.5606（3） nm^3, Dc = 1.366 g/cm^3, Z = 8, F（000） = 1104, μ（MoKα= 3.182 mm^-1, S = 0.837, the final R = 0.0460 and wR = 0.1033. Crystal X-ray diffraction analysis for 2c showed that its ring skeleton adopts [3333] conformation, in which the OH group presents at the side-exo position and the other one at the corner carbon. The 1H NMR data of 2 showed that 1-corner-R-2-side-exo-OH [3333] and 1-corner-OH-2-side-exo-R [3333] conformations coexist in dynamic equilibrium in the solution, but only the former presents in the crystal.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 robust bulky bornylimidazo[1,5-a]pyridin-3-ylidene allylic Pd complex was synthesized and well characterized.DFT calculations indicated that the ligand acts as a strongσ-donor andπ-acceptor endowing the active Pd(...A robust bulky bornylimidazo[1,5-a]pyridin-3-ylidene allylic Pd complex was synthesized and well characterized.DFT calculations indicated that the ligand acts as a strongσ-donor andπ-acceptor endowing the active Pd(0)center with high electron density and good coordination towards olefin.The introduction of a bulky,rigid bornyl ring further improved the catalytic efficacy due to the matched steric effects.This catalyst showed high efficiency and versatility in theα-arylation and Heck cyclization/Suzuki crosscoupling reactions at mild reaction conditions.Desired 3,3-disubstituted oxindoles,especially featuring an allylic-derived C3-quaternary stereocenter were obtained in high yields.Furthermore,the concise synthesis of bioactive heterocycle-fused indoline alkaloids was successfully proved.展开更多
基金supported by the National Natural Science Foundation of China(No.81974494)CAMS Innovation Fund for Medical Sciences(No.2021-I2M-1-070).
文摘Thirty-one new 10,12-disubstituted aloperine derivatives were subtly constructed through a selective oxidation on the 10-α-C-H induced by sulfonyl and a nucleophilic substitution with the stereoselectivity and scalability.Of them,compound 6b displayed a moderate anti-human coronavirus OC43(HCoV-OC43)potency and blocked the viral entry stage through a host mechanism of action.Using chemoproteomic techniques,both transmembrane serine protease 2(TMPRSS2)and scavenger receptor class B type 1(SR-B1)proteins,which act as host cofactors of viral entry,were identified to be the direct targets of 6b against HCoV-OC43.Furthermore,6b may deactivate the TMPRSS2 by inducing a change in protein conformation,rather than binding to its catalytic center,thus suppressing the viral membrane fusion.Accordingly,our study provided key scientific data for the development of aloperine derivatives into a new class of antiviral candidates against humanβ-coronavirus,including severe acute respiratory syndrome coronavirus 2(SARS-CoV-2).
文摘Sterically congested 2,2-disubstituted indane-1,3-dione derivatives have been syn-thesized and characterized by 1H NMR,13C NMR,FT-IR and elemental analysis.The B3LYP/HF calculations for computation of IR spectra have been carried out for the title compounds at the 6-31G and 6-311＋＋G basis set levels.Predicted vibrational frequencies have been assigned and compared with the experimental FT-IR spectra and they are supported each other.
文摘A strategy for the synthesis of 1,2-disubstituted benzimidazoles has been developed and a variety of 1,2-disubstituted benzimidazoles were obtained from imidoyl chlorides and o-haloanilines via copper（I）-catalyzed reaction in moderate yields.
基金Project 29932020 was supported by the National Natural Science Foundation of China.
文摘Reaction of polymer-supported a-selenoaldehydes with Grignard reagents afforded polymer-bound B-hydroxyalkyl selenides, which treated with thionyl chloride and triethylamine leading to (E)-1, 2-disubstituted ethenes in good yield.
基金Head,Department of Chemistry,Vinayakrao Patil Mahavidyala Vaijapur 423701(M.S.),India,for partial support of this work.
文摘Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted aldehydes in good to excellent isolated yields （85-95%） using water as solvent at ambient temperature. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （20--40 rain） reactions and excellent yields of products.
基金Presented in part at the Third National Symposium of the Chinese Chemical Society on Organic Chemistry, Lanzhou, China, August, 2004 (for abstract, see Chin. J. Org. Chem., 2004, Suppl. 365)This project was supported by the National Natural Science Foundation of China (No. 20072053)
文摘cis-1,2-Disubstituted cyclododecanes 2 were synthesized by sodium borohydride reduction of 2-monosubstituted cyclododecanones and their structures were confirmed by 1HNMR, ^13C NMR and elemental analysis. The higher cis-selectivity of NaBH4 reduction of 2- monosubstituted cyclododecanones was rationalized by the mode of ＂corner position carbonyl participation＂. Crystal data for 2c： Mr = 263.21, monoclinic, space group P21/c, a = 1.11140（7）, b = 2.62590（17）, c = 0.91360（6） nm, β= 106.1840（10）°, V = 2.5606（3） nm^3, Dc = 1.366 g/cm^3, Z = 8, F（000） = 1104, μ（MoKα= 3.182 mm^-1, S = 0.837, the final R = 0.0460 and wR = 0.1033. Crystal X-ray diffraction analysis for 2c showed that its ring skeleton adopts [3333] conformation, in which the OH group presents at the side-exo position and the other one at the corner carbon. The 1H NMR data of 2 showed that 1-corner-R-2-side-exo-OH [3333] and 1-corner-OH-2-side-exo-R [3333] conformations coexist in dynamic equilibrium in the solution, but only the former presents in the crystal.
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.
基金Financial supports from the National Natural Science Foundation of China(No.22101133)Natural Science Foundation of Jiangsu Province(No.BK20200768)+1 种基金Nanjing Forestry University,the National Natural Science Foundation of China(the Outstanding Youth Scholars(Overseas,2021)project)the Lab project of the State Key Laboratory of Physical Chemistry of Solid Surfaces are greatly acknowledged.
文摘A robust bulky bornylimidazo[1,5-a]pyridin-3-ylidene allylic Pd complex was synthesized and well characterized.DFT calculations indicated that the ligand acts as a strongσ-donor andπ-acceptor endowing the active Pd(0)center with high electron density and good coordination towards olefin.The introduction of a bulky,rigid bornyl ring further improved the catalytic efficacy due to the matched steric effects.This catalyst showed high efficiency and versatility in theα-arylation and Heck cyclization/Suzuki crosscoupling reactions at mild reaction conditions.Desired 3,3-disubstituted oxindoles,especially featuring an allylic-derived C3-quaternary stereocenter were obtained in high yields.Furthermore,the concise synthesis of bioactive heterocycle-fused indoline alkaloids was successfully proved.
