A novel gem-difluoromethylenated castanospermine analogue B was designed and synthesized, starting from 3-bromo-3,3-difluoropropene and L-（-）-malic acid. The key steps involve substitution cyclization reaction and R...A novel gem-difluoromethylenated castanospermine analogue B was designed and synthesized, starting from 3-bromo-3,3-difluoropropene and L-（-）-malic acid. The key steps involve substitution cyclization reaction and RCM reaction to construct the aza fused bicyclic framework.展开更多
By developing gem-difluoromethylene allenes as viable partners,regiocontrolled Rh(Ⅲ)-catalyzed redoxneutral C-C coupling/C-N cyclization has been realized to build the pyridin-2(1H)-one motifs with the embedment of a...By developing gem-difluoromethylene allenes as viable partners,regiocontrolled Rh(Ⅲ)-catalyzed redoxneutral C-C coupling/C-N cyclization has been realized to build the pyridin-2(1H)-one motifs with the embedment of a Z-configured monofluoroalkene functionality,in which either(hetero)aromatic or vinylic amides were found to be compatible.Integrated experimental and computational mechanistic studies revealed that a tandem regioselective allene 1,2-insertion/β-H elimination/hydrogen transfer/oxidative addition/cyclization/cis-β-F elimination involving an unconventional Rh(Ⅲ)-Rh(I)-Rh(Ⅲ)catalytic cycle accounts for the established transformation.Through further FMO analysis and IGMH maps,a non-covalent weak interaction network between the gem-difluoromethylene part and the OPiv moiety was rationally defined for the unconventional and specific regioselectivity control.展开更多
Seventeen novel gem-difluoromethylene-containing 1,2,3-triazoles were synthesized by the click reaction of ethyl 2-azido-2,2-difluoroacetate and terminal alkynes in the presence of 10 mol% CuI.
Ten gem-difluoromethylenated chrysin derivatives were prepared and their anticancer activities in vitro were evaluated by the standard MTT method. The results of biological test showed that some of gem-difluoromethyle...Ten gem-difluoromethylenated chrysin derivatives were prepared and their anticancer activities in vitro were evaluated by the standard MTT method. The results of biological test showed that some of gem-difluoromethylenated chrysin derivatives had higher anticancer activity than chrysin.展开更多
基金the National Natural Science Foundation of China (Nos. 21272036, 21332010)the National Basic Research Program of China (No. 2012CB21600)
文摘A novel gem-difluoromethylenated castanospermine analogue B was designed and synthesized, starting from 3-bromo-3,3-difluoropropene and L-（-）-malic acid. The key steps involve substitution cyclization reaction and RCM reaction to construct the aza fused bicyclic framework.
基金the National Natural Science Foundation of China(NSFC,Nos.21877020,22007020)Natural Science Foundation of Guangdong Province(No.2019A1515010935)Science and Technology Program of Guangzhou(No.202102020615)for financial support on this study。
文摘By developing gem-difluoromethylene allenes as viable partners,regiocontrolled Rh(Ⅲ)-catalyzed redoxneutral C-C coupling/C-N cyclization has been realized to build the pyridin-2(1H)-one motifs with the embedment of a Z-configured monofluoroalkene functionality,in which either(hetero)aromatic or vinylic amides were found to be compatible.Integrated experimental and computational mechanistic studies revealed that a tandem regioselective allene 1,2-insertion/β-H elimination/hydrogen transfer/oxidative addition/cyclization/cis-β-F elimination involving an unconventional Rh(Ⅲ)-Rh(I)-Rh(Ⅲ)catalytic cycle accounts for the established transformation.Through further FMO analysis and IGMH maps,a non-covalent weak interaction network between the gem-difluoromethylene part and the OPiv moiety was rationally defined for the unconventional and specific regioselectivity control.
基金Project supported by the National Natural Science Foundation of China （No. 21072057）, the Key Project in the National Science ＆ Technology Pillar Program of China in the Twelfth Five-year Plan Period （No. 2011BAE06B05）, and the Shanghai Leading Academic Discipline Project （No. B507）.
文摘Seventeen novel gem-difluoromethylene-containing 1,2,3-triazoles were synthesized by the click reaction of ethyl 2-azido-2,2-difluoroacetate and terminal alkynes in the presence of 10 mol% CuI.
文摘Ten gem-difluoromethylenated chrysin derivatives were prepared and their anticancer activities in vitro were evaluated by the standard MTT method. The results of biological test showed that some of gem-difluoromethylenated chrysin derivatives had higher anticancer activity than chrysin.
