A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition m...A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .展开更多
Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.
Microwave irradiation can accelerate the rate of the synthetic reaction of α,β-unsaturated ketones by using KF-Al2O3 as catalyst. The rate enhancement of the reaction is 360-860 fold.
In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects o...In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.展开更多
Jiu Ai Tu(The Moxa Treatment)from the Song dynasty is the earliest surviving painting that focuses on the subject of acupuncture and moxibustion.This paper takes the medical activities depicted in the artwork as its r...Jiu Ai Tu(The Moxa Treatment)from the Song dynasty is the earliest surviving painting that focuses on the subject of acupuncture and moxibustion.This paper takes the medical activities depicted in the artwork as its research object and systematically analyzes the external treatment methods for abscesses during the Song dynasty reflected in Jiu Ai Tu.By examining the understanding of abscesses during that period,the paper explores the level of development in external medicine techniques.By analyzing the medical awareness and behaviors of patients when facing such severe illnesses,it aims to explore the societal cognition and experiences regarding health and disease.The paper attempts to present the folk medical ecology of the Song dynasty represented by Jiu Ai Tu.展开更多
Acetals and ketals are among the important materials of organic synthesis and as protecting agent of carbonyl functionality. A milder, efficient and green synthesis of acetals and ketals has been developed using Silic...Acetals and ketals are among the important materials of organic synthesis and as protecting agent of carbonyl functionality. A milder, efficient and green synthesis of acetals and ketals has been developed using Silicotungstic acid modified Bentonite (STA-Ben) as a catalyst. STA-Ben has been synthesized and characterized by various analytical techniques. It has been found to be an efficient and reusable catalyst for the synthesis of acetyl derivatives in excellent yields. In order to elucidate the efficiency of the STA-Ben as catalyst, reaction has also been performed using various catalysts. The reaction conditions (time and amount of catalyst) have been optimized using various catalysts. The products of the various reactions have been characterized by FT-IR, NMR.展开更多
Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes high...Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.展开更多
By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and op...By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and optical yield in the presence of chiral catalysts展开更多
An unusual reduction of some aromatic aldehydes and ketones by sodium borohydride was discovered.In a THF/H2O or DMSO/H2O solvent system the aromatic aldehydes and ketones with acyloxy substituent on the orthoposition...An unusual reduction of some aromatic aldehydes and ketones by sodium borohydride was discovered.In a THF/H2O or DMSO/H2O solvent system the aromatic aldehydes and ketones with acyloxy substituent on the orthoposition to the carbonyl group can be reduced to the corresponding alkyl phenols.This unusual reduction is applicable also to the corresponding alcohols of all the above aldehydes and ketones.A putative mechanism was suggested.In addition to the above aldehydes,ketones and benzyl alcohols,certain 4acyloxybenzyl esters(probably also the 2substituted analogues)such as 4benzoyloxybenzyl benzoate was also found to be reduced to methylphenol by this unusual reduction.展开更多
Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
Objective:To determine the active components of Eupolyphaga sinensis Walker(Tu Bie Chong)and explore the mechanisms underlying its fracture-healing ability.Methods: A modified Einhorn method was used to develop a rat ...Objective:To determine the active components of Eupolyphaga sinensis Walker(Tu Bie Chong)and explore the mechanisms underlying its fracture-healing ability.Methods: A modified Einhorn method was used to develop a rat tibial fracture model.Progression of bone healing was assessed using radiological methods.Safranin O/fast green and CD31 immunohistochemical staining were performed to evaluate the growth of bone cells and angiogenesis at the fracture site.Methylthiazoletetrazolium blue and wound healing assays were used to analyze cell viability and migration.The Transwell assay was used to explore the invasion capacity of the cells.Tubule formation assays were used to assess the angiogenesis capacity of human vascular endothelial cells(HUVECs).qRT-PCR was used to evaluate the changes in gene transcription levels.Results: Tu Bie Chong fraction 3(TF3)significantly shortened the fracture healing time in model rats.X-ray results showed that on day 14,fracture healing in the TF3 treatment group was significantly better than that in the control group(P=.0086).Tissue staining showed that cartilage growth and the number of H-shaped blood vessels at the fracture site of the TF3 treatment group were better than those of the control group.In vitro,TF3 significantly promoted the proliferation and wound healing of MC3T3-E1s and HUVECs(all P<.01).Transwell assays showed that TF3 promoted the migration of HUVECs,but inhibited the migration of MC3T3-E1 cells.Tubule formation experiments confirmed that TF3 markedly promoted the ability of vascular endothelial cells to form microtubules.Gene expression analysis revealed that TF3 significantly promoted the expression of VEGFA,SPOCD1,NGF,and NGFR in HUVECs.In MC3T3-E1 cells,the transcript levels of RUNX2 and COL2A1 were significantly elevated following TF3 treatment.Conclusion: TF3 promotes fracture healing by promoting bone regeneration associated with the RUNX2 pathway and angiogenesis associated with the VEGFA pathway.展开更多
The substituted cyclopentadienyl-magnesium-chloride, obtained by exocyclic addition of 6,6-dialkylfulvene and allyl-magnesium-chloride, reacted with the ketone 3, the product was hydrolyzed and dehydrated to give the ...The substituted cyclopentadienyl-magnesium-chloride, obtained by exocyclic addition of 6,6-dialkylfulvene and allyl-magnesium-chloride, reacted with the ketone 3, the product was hydrolyzed and dehydrated to give the 2-(1 ,1-dialkyl-3-butenyl)-6,6-dialkyl-fulvene 5. The structure of 5 was determined by using the 1H NMR spectra of 5 and the adducts of 5 with tetracyanoethylene.展开更多
The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained,...The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.展开更多
The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated...The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated ketones, and the activity of catalysts P-1.80-Ni, P-2 00-Ni or P-1.80(2 00) -Ni-M(M: Pd, Co, Cu) in the selective hydrogenation of carbon carbon double bonds in α,β-unsaturated carboxylic esters, were investigated systematically. According to the experimental results, the selectivities of these catalysts toward the hydrogenation of the carbon carbon double bonds of α,β-unsaturated keones or α,β-unsaturated carboxylic esters are 96%—100% or 100%, respectively.展开更多
Regio and stereoselective synthesis of substituted dihydrofurans were accomplished by eeric ammonium nitrate mediated oxidative cycloaddition of 1,3-dicarbonyls to β-aryl-α,β-unsaturated ketones in moderate yields.
文摘A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .
基金support by the Natural Science Foundation of Zhejiang Province(No.Y4051137,Y405015 and Y4080177)
文摘Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.
文摘Microwave irradiation can accelerate the rate of the synthetic reaction of α,β-unsaturated ketones by using KF-Al2O3 as catalyst. The rate enhancement of the reaction is 360-860 fold.
基金the NSFC(No.20272037),the Doctor's Foundation of Education Ministry of China(No.20030610022)Foundation of Xihua University(No.R0723315) and(No.07ZA109) for the financial support of this work.
文摘In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.
基金financed from the grant of the National Social Science Foundation General Project(No.23BZS010)。
文摘Jiu Ai Tu(The Moxa Treatment)from the Song dynasty is the earliest surviving painting that focuses on the subject of acupuncture and moxibustion.This paper takes the medical activities depicted in the artwork as its research object and systematically analyzes the external treatment methods for abscesses during the Song dynasty reflected in Jiu Ai Tu.By examining the understanding of abscesses during that period,the paper explores the level of development in external medicine techniques.By analyzing the medical awareness and behaviors of patients when facing such severe illnesses,it aims to explore the societal cognition and experiences regarding health and disease.The paper attempts to present the folk medical ecology of the Song dynasty represented by Jiu Ai Tu.
文摘Acetals and ketals are among the important materials of organic synthesis and as protecting agent of carbonyl functionality. A milder, efficient and green synthesis of acetals and ketals has been developed using Silicotungstic acid modified Bentonite (STA-Ben) as a catalyst. STA-Ben has been synthesized and characterized by various analytical techniques. It has been found to be an efficient and reusable catalyst for the synthesis of acetyl derivatives in excellent yields. In order to elucidate the efficiency of the STA-Ben as catalyst, reaction has also been performed using various catalysts. The reaction conditions (time and amount of catalyst) have been optimized using various catalysts. The products of the various reactions have been characterized by FT-IR, NMR.
基金the Higher Committee for Education Development in Iraq for financial support(AHB)the Commonwealth Scholarships Commission in the UK for a Split-Site PhD Scholarship(RB)
文摘Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.
文摘By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and optical yield in the presence of chiral catalysts
文摘An unusual reduction of some aromatic aldehydes and ketones by sodium borohydride was discovered.In a THF/H2O or DMSO/H2O solvent system the aromatic aldehydes and ketones with acyloxy substituent on the orthoposition to the carbonyl group can be reduced to the corresponding alkyl phenols.This unusual reduction is applicable also to the corresponding alcohols of all the above aldehydes and ketones.A putative mechanism was suggested.In addition to the above aldehydes,ketones and benzyl alcohols,certain 4acyloxybenzyl esters(probably also the 2substituted analogues)such as 4benzoyloxybenzyl benzoate was also found to be reduced to methylphenol by this unusual reduction.
基金supported by the National Natural Science Foundation of China(No.29772007)
文摘Phenylseleno and sulfonyl substituted allyl alcohols were synthesized stereoselectively by the three-component reaction of acetylenic sulfone, phenylselenomagnesium bromide and ketones in one-pot.
基金supported by“the Fundamental Research Funds for the Central Universities”(2020-JYB-ZDGG-054)“Beijing university of Chinese medicine XINAO Award Fund”(2019)Beijing University of Chinese Medicine Scientific Research and Development Fund(2170072220002).
文摘Objective:To determine the active components of Eupolyphaga sinensis Walker(Tu Bie Chong)and explore the mechanisms underlying its fracture-healing ability.Methods: A modified Einhorn method was used to develop a rat tibial fracture model.Progression of bone healing was assessed using radiological methods.Safranin O/fast green and CD31 immunohistochemical staining were performed to evaluate the growth of bone cells and angiogenesis at the fracture site.Methylthiazoletetrazolium blue and wound healing assays were used to analyze cell viability and migration.The Transwell assay was used to explore the invasion capacity of the cells.Tubule formation assays were used to assess the angiogenesis capacity of human vascular endothelial cells(HUVECs).qRT-PCR was used to evaluate the changes in gene transcription levels.Results: Tu Bie Chong fraction 3(TF3)significantly shortened the fracture healing time in model rats.X-ray results showed that on day 14,fracture healing in the TF3 treatment group was significantly better than that in the control group(P=.0086).Tissue staining showed that cartilage growth and the number of H-shaped blood vessels at the fracture site of the TF3 treatment group were better than those of the control group.In vitro,TF3 significantly promoted the proliferation and wound healing of MC3T3-E1s and HUVECs(all P<.01).Transwell assays showed that TF3 promoted the migration of HUVECs,but inhibited the migration of MC3T3-E1 cells.Tubule formation experiments confirmed that TF3 markedly promoted the ability of vascular endothelial cells to form microtubules.Gene expression analysis revealed that TF3 significantly promoted the expression of VEGFA,SPOCD1,NGF,and NGFR in HUVECs.In MC3T3-E1 cells,the transcript levels of RUNX2 and COL2A1 were significantly elevated following TF3 treatment.Conclusion: TF3 promotes fracture healing by promoting bone regeneration associated with the RUNX2 pathway and angiogenesis associated with the VEGFA pathway.
基金Supported by the National Natural Science Foundation of Shandong Province
文摘The substituted cyclopentadienyl-magnesium-chloride, obtained by exocyclic addition of 6,6-dialkylfulvene and allyl-magnesium-chloride, reacted with the ketone 3, the product was hydrolyzed and dehydrated to give the 2-(1 ,1-dialkyl-3-butenyl)-6,6-dialkyl-fulvene 5. The structure of 5 was determined by using the 1H NMR spectra of 5 and the adducts of 5 with tetracyanoethylene.
文摘The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.
文摘The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated ketones, and the activity of catalysts P-1.80-Ni, P-2 00-Ni or P-1.80(2 00) -Ni-M(M: Pd, Co, Cu) in the selective hydrogenation of carbon carbon double bonds in α,β-unsaturated carboxylic esters, were investigated systematically. According to the experimental results, the selectivities of these catalysts toward the hydrogenation of the carbon carbon double bonds of α,β-unsaturated keones or α,β-unsaturated carboxylic esters are 96%—100% or 100%, respectively.
文摘Regio and stereoselective synthesis of substituted dihydrofurans were accomplished by eeric ammonium nitrate mediated oxidative cycloaddition of 1,3-dicarbonyls to β-aryl-α,β-unsaturated ketones in moderate yields.
