In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respective...In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respectively in moderate to good yields.展开更多
A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly ...A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly functionalized 2-cyanopyrroles are constructed efficiently through a new formal [3 + 2] mode, demonstrating diverse reactivity and synthetic utility in organic chemistry. 2-Cyanopyrrole is converted into a nucleobase analogue of Remdesivir and 5H-pyrrolo[2,1-a]isoindole through a three-step or a two-step sequence, respectively. This protocol features broad substrate scope, operational simplicity and good functional group tolerance.展开更多
Comprehensive Summary Pd-catalyzed asymmetric allylic C—H functionalization has emerged as a powerful tool to access chiral,densely functionalized molecules from easily accessible alkenes,enabling the increase of the...Comprehensive Summary Pd-catalyzed asymmetric allylic C—H functionalization has emerged as a powerful tool to access chiral,densely functionalized molecules from easily accessible alkenes,enabling the increase of the step-or atom-economy by minimizing functional group manipulations for preparing allylating reagents.Due to the inadequacy of stereoselection strategies,the asymmetric allylic C—H functionalization is still in the early stage.In this essay,we will describe our journey to identification of asymmetric catalytic systems,mechanism of allylic C—H activation,control of stereo-and regioselectivity,and applications in asymmetric synthesis.展开更多
AIM: To develop and optimize cDNA representational difference analysis (cDNA RDA) method and to identify and clone garlic up-regulated genes in human gastric cancer (HGC) cells. METHODS: We performed cDNA RDA method b...AIM: To develop and optimize cDNA representational difference analysis (cDNA RDA) method and to identify and clone garlic up-regulated genes in human gastric cancer (HGC) cells. METHODS: We performed cDNA RDA method by using abundant double-stranded cDNA messages provided by two self-constructed cDNA libraries (Allitridi-treated and paternal HGC cell line BGC823 cells cDNA libraries respectively). Bam H I and Xho I restriction sites harbored in the library vector were used to select representations. Northern and Slot blots analyses were employed to identify the obtained difference products. RESULTS: Fragments released from the cDNA library vector after restriction endonuclease digestion acted as good marker indicating the appropriate digestion degree for library DNA. Two novel expressed sequence tags (ESTs) and a recombinant gene were obtained. Slot blots result showed a 8-fold increase of glia-derived nexin/protease nexin 1 (GDN/PN1) gene expression level and 4-fold increase of hepatitis B virus x-interacting protein (XIP) mRNA level in BGC823 cells after Allitridi treatment for 72h. CONCLUSION: Elevated levels of GDN/PN1 and XIP mRNAs induced by Allitridi provide valuable molecular evidence for elucidating the garlic's efficacies against neurodegenerative and inflammatory diseases. Isolation of a recombinant gene and two novel ESTs further show cDNA RDA based on cDNA libraries to be a powerful method with high specificity and reproducibility in cloning differentially expressed genes.展开更多
To investigate the therapeutic effects and mechanisms of garlicin for treatment of unstable angina pectoris (UAP), garlicin injectio was intravenously dripped 60 mg/day in 34 cases for 10 days. Nitroglycerine was used...To investigate the therapeutic effects and mechanisms of garlicin for treatment of unstable angina pectoris (UAP), garlicin injectio was intravenously dripped 60 mg/day in 34 cases for 10 days. Nitroglycerine was used in 21 cases of the control group. The results showed that the total effective rates in improving symptoms and electrocardiogram after garlicin treatment were respectively 82% and 62%, and that the plasma endothelin and blood sugar levels were markedly lowered in cases with hyperglycemia.展开更多
ein a Pd-catalyzed intramolecular allylation reaction of unprotected allylic alcohols was developed,and the reaction proceeded through a Pd(Ⅱ)-mediated allylic carbocation species formation,followed by a Friedel-Cr...ein a Pd-catalyzed intramolecular allylation reaction of unprotected allylic alcohols was developed,and the reaction proceeded through a Pd(Ⅱ)-mediated allylic carbocation species formation,followed by a Friedel-Crafts type annulation to afford functionalized chromanes.展开更多
Palladium-catalyzed allylation of carbonucleophiles has been widely used for carbon-carbon bond formation.Among the allylic compounds studied,allylic acetates were mostwidely used as precursors of(π-allyl)palladium i...Palladium-catalyzed allylation of carbonucleophiles has been widely used for carbon-carbon bond formation.Among the allylic compounds studied,allylic acetates were mostwidely used as precursors of(π-allyl)palladium intermediates.However,bases such as NaHmust be used to generate anions in this reaction.Recently,research on carrying out the palla-展开更多
In many reactions involving selenosulfonate or thiosulfonate,the sutfone group often leaves in form of benzenesutfinic acid or sodium benzenesulfinate.A one-pot two-step reaction of selenosulfonate with isocyanides an...In many reactions involving selenosulfonate or thiosulfonate,the sutfone group often leaves in form of benzenesutfinic acid or sodium benzenesulfinate.A one-pot two-step reaction of selenosulfonate with isocyanides and allyl alcohol under aqueous conditions to afford selenocarbamates and allyl sulfone compounds is reported.The sulfinic acid as the first-step side product is converted to the allyl sulfone compound by water promoted reaction with allyl alcohol.Water acts as both an oxygen source of selenocarbamates and as a promoter to drive the second step reactio n.The reactions have the advantages of mild conditions,green,environment-friendly,and high atomic economy.展开更多
基金the Natural Science Foundation of the Education Commission of Jiangsu Province
文摘In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respectively in moderate to good yields.
基金the National Natural Science Foundation of China(Nos.22171178, 21871174, 22071143)Innovation Program of Shanghai Municipal Education Commission (No.2019–01–07–00–09-E00008) for financial support。
文摘A facile Tf OH-catalyzed oxidative cyclization of allyl compounds and isocyanide has been developed with the assistance of DDQ, where isocyanide is used as the crucial "N" and "CN" sources. Highly functionalized 2-cyanopyrroles are constructed efficiently through a new formal [3 + 2] mode, demonstrating diverse reactivity and synthetic utility in organic chemistry. 2-Cyanopyrrole is converted into a nucleobase analogue of Remdesivir and 5H-pyrrolo[2,1-a]isoindole through a three-step or a two-step sequence, respectively. This protocol features broad substrate scope, operational simplicity and good functional group tolerance.
基金the National Key R&D Program of China(2021YFA1500100)Youth Innovation Promotion Association CAS(2020448)+3 种基金NSFC(22171254 and 22188101)Anhui Provincial Natural Science Foundation(2108085MB58)USTC Research Funds of the DoubleFirst-Class Initiative(YD2060002024)Start-up Research Fund from University of Science and Technology of China(KY2060000216).
文摘Comprehensive Summary Pd-catalyzed asymmetric allylic C—H functionalization has emerged as a powerful tool to access chiral,densely functionalized molecules from easily accessible alkenes,enabling the increase of the step-or atom-economy by minimizing functional group manipulations for preparing allylating reagents.Due to the inadequacy of stereoselection strategies,the asymmetric allylic C—H functionalization is still in the early stage.In this essay,we will describe our journey to identification of asymmetric catalytic systems,mechanism of allylic C—H activation,control of stereo-and regioselectivity,and applications in asymmetric synthesis.
基金the Natural Scientific Foundation of China (NSFC3962526)National High-Technology Project-863 (102-10-01-04)
文摘AIM: To develop and optimize cDNA representational difference analysis (cDNA RDA) method and to identify and clone garlic up-regulated genes in human gastric cancer (HGC) cells. METHODS: We performed cDNA RDA method by using abundant double-stranded cDNA messages provided by two self-constructed cDNA libraries (Allitridi-treated and paternal HGC cell line BGC823 cells cDNA libraries respectively). Bam H I and Xho I restriction sites harbored in the library vector were used to select representations. Northern and Slot blots analyses were employed to identify the obtained difference products. RESULTS: Fragments released from the cDNA library vector after restriction endonuclease digestion acted as good marker indicating the appropriate digestion degree for library DNA. Two novel expressed sequence tags (ESTs) and a recombinant gene were obtained. Slot blots result showed a 8-fold increase of glia-derived nexin/protease nexin 1 (GDN/PN1) gene expression level and 4-fold increase of hepatitis B virus x-interacting protein (XIP) mRNA level in BGC823 cells after Allitridi treatment for 72h. CONCLUSION: Elevated levels of GDN/PN1 and XIP mRNAs induced by Allitridi provide valuable molecular evidence for elucidating the garlic's efficacies against neurodegenerative and inflammatory diseases. Isolation of a recombinant gene and two novel ESTs further show cDNA RDA based on cDNA libraries to be a powerful method with high specificity and reproducibility in cloning differentially expressed genes.
文摘To investigate the therapeutic effects and mechanisms of garlicin for treatment of unstable angina pectoris (UAP), garlicin injectio was intravenously dripped 60 mg/day in 34 cases for 10 days. Nitroglycerine was used in 21 cases of the control group. The results showed that the total effective rates in improving symptoms and electrocardiogram after garlicin treatment were respectively 82% and 62%, and that the plasma endothelin and blood sugar levels were markedly lowered in cases with hyperglycemia.
文摘ein a Pd-catalyzed intramolecular allylation reaction of unprotected allylic alcohols was developed,and the reaction proceeded through a Pd(Ⅱ)-mediated allylic carbocation species formation,followed by a Friedel-Crafts type annulation to afford functionalized chromanes.
文摘Palladium-catalyzed allylation of carbonucleophiles has been widely used for carbon-carbon bond formation.Among the allylic compounds studied,allylic acetates were mostwidely used as precursors of(π-allyl)palladium intermediates.However,bases such as NaHmust be used to generate anions in this reaction.Recently,research on carrying out the palla-
基金the National Natural Science Foundation of China (Nos.21971174,21772137,21672157)the Ph.D.Programs Foundation of PAPD+2 种基金the Project of Scientific and Technologic Infrastructure of Suzhou (No.SZS201708)the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 16KJA150002)Soochow University,and State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials for financial support。
文摘In many reactions involving selenosulfonate or thiosulfonate,the sutfone group often leaves in form of benzenesutfinic acid or sodium benzenesulfinate.A one-pot two-step reaction of selenosulfonate with isocyanides and allyl alcohol under aqueous conditions to afford selenocarbamates and allyl sulfone compounds is reported.The sulfinic acid as the first-step side product is converted to the allyl sulfone compound by water promoted reaction with allyl alcohol.Water acts as both an oxygen source of selenocarbamates and as a promoter to drive the second step reactio n.The reactions have the advantages of mild conditions,green,environment-friendly,and high atomic economy.