Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A w...Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A wide diversity of aliphatic silanes have been prepared from terminal alkenes,aryl halides and Suginome’s reagent.This protocol is highlighted by excellent regioselectivity,mild reaction conditions and good functional group tolerance.In addition to benzylic positions,carbon–carbon bonds can also be constructed at allylic positions.Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome’s reagent,and the addition of a Pyr Ox ligand inhibits the formation of side-products from the carbon-Heck pathway.Moreover,studies toward the nature of the Pyr Ox ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain–walking process,but not the arylation step.展开更多
Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difu...Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.展开更多
A stimuli-responsive supramolecular polymer network has been constructed based on the host-guest interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction guest G2.The form...A stimuli-responsive supramolecular polymer network has been constructed based on the host-guest interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction guest G2.The formation mechanism of the supramolecular polymer network has been explored by the intensive study.With the addition of the competitive molecules and heating,the supramolecular polymer network could be dissociated and lead to clear changes in NMR spectroscopy and viscosity property.展开更多
The reactive oxygen species(ROS) are tightly associated with endoplasmic reticulum(ER) stress.Thus,the deep and visual insight of aberrant ROS fluctuations in the ER can help us better investigate the ER stress-associ...The reactive oxygen species(ROS) are tightly associated with endoplasmic reticulum(ER) stress.Thus,the deep and visual insight of aberrant ROS fluctuations in the ER can help us better investigate the ER stress-associated pathology.In this work,a fluorescent probe ERC for HOCI detection in the ER based on phenothiazine-derived coumarin platform was developed.In the presence of HOCI,ERC exhibited an emission change from 609 nm to 503 nm within seconds.It also showed high sensitivity(0.44 μmol/L)and superb photostability.Significantly,ERC displayed low cytotoxicity,good cell membrane permeability,and appreciable ER-targetability.Ultimately,the probe was successfully utilized to image exogenous and endogenous HOCl in living cells and reveal the HOCI burst in cisplatin-treated cancer cells.展开更多
基金supported by the National Natural Science Foundation of China(21702151,21774029,and 21871211)the Fundamental Research Funds for Central Universities(2042019kf0208)。
文摘Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A wide diversity of aliphatic silanes have been prepared from terminal alkenes,aryl halides and Suginome’s reagent.This protocol is highlighted by excellent regioselectivity,mild reaction conditions and good functional group tolerance.In addition to benzylic positions,carbon–carbon bonds can also be constructed at allylic positions.Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome’s reagent,and the addition of a Pyr Ox ligand inhibits the formation of side-products from the carbon-Heck pathway.Moreover,studies toward the nature of the Pyr Ox ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain–walking process,but not the arylation step.
基金supported by the National Natural Science Foundation of China (21871211, 21774029, 22122107)the Fundamental Research Funds for Central Universities (2042019kf0208)。
文摘Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.
基金supported by National Natural Science Foundation of China(Nos.21702153 and 21801194).
文摘A stimuli-responsive supramolecular polymer network has been constructed based on the host-guest interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction guest G2.The formation mechanism of the supramolecular polymer network has been explored by the intensive study.With the addition of the competitive molecules and heating,the supramolecular polymer network could be dissociated and lead to clear changes in NMR spectroscopy and viscosity property.
基金This work was supported by the Hubei Provincial Department of Education Science and Technology Research Projects(No.Q20182704).
文摘The reactive oxygen species(ROS) are tightly associated with endoplasmic reticulum(ER) stress.Thus,the deep and visual insight of aberrant ROS fluctuations in the ER can help us better investigate the ER stress-associated pathology.In this work,a fluorescent probe ERC for HOCI detection in the ER based on phenothiazine-derived coumarin platform was developed.In the presence of HOCI,ERC exhibited an emission change from 609 nm to 503 nm within seconds.It also showed high sensitivity(0.44 μmol/L)and superb photostability.Significantly,ERC displayed low cytotoxicity,good cell membrane permeability,and appreciable ER-targetability.Ultimately,the probe was successfully utilized to image exogenous and endogenous HOCl in living cells and reveal the HOCI burst in cisplatin-treated cancer cells.
