Development of the high activity,promoter‐free catalysts for carbonyl sulfide(COS)hydrolysis is important for the efficient utilization of various feedstocks.In this study,the Cu‐based metal‐organic framework HKUST...Development of the high activity,promoter‐free catalysts for carbonyl sulfide(COS)hydrolysis is important for the efficient utilization of various feedstocks.In this study,the Cu‐based metal‐organic framework HKUST‐1is synthesized by a simple and mild anodic‐dissolution electrochemical method.The physical and chemical properties of the samples are characterized by several techniques,including scanning electron microscopy,X‐ray diffraction,Brunauer‐Emmett‐Teller analysis and X‐ray photoelectron spectroscopy.The results reveal that the synthesis voltage plays a crucial role in controlling the morphology of the resulting HKUST‐1.The obtained samples function as novel catalysts for the hydrolysis of COS.A high efficiency,approaching100%,can be achieved for the conversion of COS at150oC over the optimal HKUST‐1synthesized at25V.This is significantly higher than that of the sample prepared by the traditional hydrothermal method.Additionally,the effects of the water temperature and the flow velocity on the hydrolysis of COS are also investigated in detail.Finally,a possible reaction pathway of COS hydrolysis over HKUST‐1is also proposed.This work represents the first example of MOFs applied to the catalytic hydrolysis of COS.The results presented in this study can be anticipated to give a feasible impetus to design novel catalysts for removing the sulfur‐containing compounds.展开更多
The term polychlorinated biphenyls, or PCBs refers to a class of synthetic organic chemicals that are, to a large degree, chemically inert. PCBs are not found in a nature as a natural compounds and its appearance in n...The term polychlorinated biphenyls, or PCBs refers to a class of synthetic organic chemicals that are, to a large degree, chemically inert. PCBs are not found in a nature as a natural compounds and its appearance in natural environment is connected with unintentional and irresponsible human activity. PCBs have been produced on an industrial scale for more than 50 years and have been exported as chemicals in products to almost every country in the world. PCBs were commonly used as dielectric fluids in transformers and capacitors, in heat transfer and hydraulic systems. Other uses of PCBs included the formulation of lubricating and cutting oils, as plasticizers in paints. Nowadays PCBs are ranked among the compounds called POP (Persistent Organic Pollutants). This group of hazard removable pollutants includes pesticides, dioxins and furans also. Fishes fished from August 2006 to December 2007 from lakes in north-east Poland: Lafiskie, Kisajno and Niegocin. The investigations were carried out on four fish species: roach, common bream, perch and pike. According to the preliminary mass and length measurements anticipatory treatment were realized. Subsequently fishes were analysed in accordance with National Institute of Hygiene method. According to the investigations results PCBs were found in fish muscular tissues, fished from north-east lakes. PCB level didn't exceed the highest acceptable daily dose (4pg-TEQ body mass/day).展开更多
The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N (nitrogen) atoms have been replac...The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N (nitrogen) atoms have been replaced on atoms of P (phosphorus), As (arsenic), Sb (antimony) and Bi (bismuth). The authors have proposed a new mechanism for the possible reactions.展开更多
This paper is a result of a review through 25 papers on the synthesis of three-, four-, five-, six-, and seven-membered rings on solid support. Solid-phase organic synthesis methods that enable the rapid production of...This paper is a result of a review through 25 papers on the synthesis of three-, four-, five-, six-, and seven-membered rings on solid support. Solid-phase organic synthesis methods that enable the rapid production of arrays of heterocycles are of critical importance to the pharmaceutical industry. The generation of heterocyclic chemistry by solid-phase synthesis will definitely accelerate the development of pharmaceutical research.展开更多
Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical...Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.展开更多
Total syntheses of terpenoids play an essential role in the development of synthetic organic chemistry and medicinal science.Chinese synthetic community has made more and more profound contribution to this field and h...Total syntheses of terpenoids play an essential role in the development of synthetic organic chemistry and medicinal science.Chinese synthetic community has made more and more profound contribution to this field and has gradually grown into a major force in the world over the past years. In this review, we shall celebrate the achievement by surveying the recent terpenoid syntheses from China since 2010.展开更多
Benzoxaborole,as a versatile scaffold,plays important roles in organic synthesis,molecular recognition and supramolecular chemistry.It is also a privileged structure in medicinal chemistry due to its desirable physico...Benzoxaborole,as a versatile scaffold,plays important roles in organic synthesis,molecular recognition and supramolecular chemistry.It is also a privileged structure in medicinal chemistry due to its desirable physicochemical and drug-like properties.Recently,benzoxaboroles were widely applied as antifungal,antibacterial,antiviral,anti-parasite,and anti-inflammatory agents.This review covers the properties,synthetic methods and applications of benzoxaboroles in medicinal chemistry.展开更多
Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n...Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n(M=metal;L=ligand),the corresponding organometallic complex was called metallafuran,which should be two possible isomers called a-metallafuran(metal fragment at a-carbon of original furan)and b-metallafuran(metal fragment at b-carbon of original furan).As an organometallic complex,a-metallafuran has two resonant forms:one can be viewed as carbonyl coordinated vinyl metal complex and the other can be viewed as alkoxymetal carbene.Therefore,a-metallafuran was also called chelated vinyl ketone metal complex or oxametallacyclopentadiene in the early literatures.For synthesis of metallafurans,a-metallafurans were very common and easily prepared,for example,from alkynes insertion into acyl metal complexes and so on.While there were rare examples reported for b-metallafurans.In this mini review,the synthetic chemistry of metallafuran was mainly focused on its formation mechanism.展开更多
The sustainable development of our future represents an unorthodox challenge in sciences and technologies.The exploration of unconventional chemical reactivities that could potentially result in more sustainable chemi...The sustainable development of our future represents an unorthodox challenge in sciences and technologies.The exploration of unconventional chemical reactivities that could potentially result in more sustainable chemical productions with efficient utilization of resource and inherent prevention of waste will provide the foundation for the synthetic chemistry of our future.As part of this endeavor,we have explored metal-mediated reactions in water to minimize protection-deprotection and the use of organic solvents,catalytic nucleophilic additions via C-H reactions to avoid generation and use of stoichiometric organic halides and metal in water,and Cross-Dehydrogenative-Coupling(CDC) reactions to minimize overall transformation steps.展开更多
Umpolung is a fundamental concept in organic chemistry, which provides an alternative strategy for the synthesis of target compounds which were not easily accessible by conventional methods. Herein, a mild and efficie...Umpolung is a fundamental concept in organic chemistry, which provides an alternative strategy for the synthesis of target compounds which were not easily accessible by conventional methods. Herein, a mild and efficient PhI(OAc)_2-promoted umpolung acetoxylation reactions of enamides was developed for the synthesis of α-acetoxy ketones. The reaction tolerates a wide range of functional groups and affords α-acetoxy ketones in good to excellent yields. PhI(OAc)_2 serves as a source of acetoxy in the reaction.展开更多
基金supported by the National Natural Science Foundation of China (21603034,21576051)the National High Technology Research and Development Program of China (863 Program,2015AA03A402)~~
文摘Development of the high activity,promoter‐free catalysts for carbonyl sulfide(COS)hydrolysis is important for the efficient utilization of various feedstocks.In this study,the Cu‐based metal‐organic framework HKUST‐1is synthesized by a simple and mild anodic‐dissolution electrochemical method.The physical and chemical properties of the samples are characterized by several techniques,including scanning electron microscopy,X‐ray diffraction,Brunauer‐Emmett‐Teller analysis and X‐ray photoelectron spectroscopy.The results reveal that the synthesis voltage plays a crucial role in controlling the morphology of the resulting HKUST‐1.The obtained samples function as novel catalysts for the hydrolysis of COS.A high efficiency,approaching100%,can be achieved for the conversion of COS at150oC over the optimal HKUST‐1synthesized at25V.This is significantly higher than that of the sample prepared by the traditional hydrothermal method.Additionally,the effects of the water temperature and the flow velocity on the hydrolysis of COS are also investigated in detail.Finally,a possible reaction pathway of COS hydrolysis over HKUST‐1is also proposed.This work represents the first example of MOFs applied to the catalytic hydrolysis of COS.The results presented in this study can be anticipated to give a feasible impetus to design novel catalysts for removing the sulfur‐containing compounds.
文摘The term polychlorinated biphenyls, or PCBs refers to a class of synthetic organic chemicals that are, to a large degree, chemically inert. PCBs are not found in a nature as a natural compounds and its appearance in natural environment is connected with unintentional and irresponsible human activity. PCBs have been produced on an industrial scale for more than 50 years and have been exported as chemicals in products to almost every country in the world. PCBs were commonly used as dielectric fluids in transformers and capacitors, in heat transfer and hydraulic systems. Other uses of PCBs included the formulation of lubricating and cutting oils, as plasticizers in paints. Nowadays PCBs are ranked among the compounds called POP (Persistent Organic Pollutants). This group of hazard removable pollutants includes pesticides, dioxins and furans also. Fishes fished from August 2006 to December 2007 from lakes in north-east Poland: Lafiskie, Kisajno and Niegocin. The investigations were carried out on four fish species: roach, common bream, perch and pike. According to the preliminary mass and length measurements anticipatory treatment were realized. Subsequently fishes were analysed in accordance with National Institute of Hygiene method. According to the investigations results PCBs were found in fish muscular tissues, fished from north-east lakes. PCB level didn't exceed the highest acceptable daily dose (4pg-TEQ body mass/day).
文摘The authors spent the search for new methods of synthesis possible of organometallic compounds of phosphorus, arsenic, antimony, bismuth. For modifications classical reactions the N (nitrogen) atoms have been replaced on atoms of P (phosphorus), As (arsenic), Sb (antimony) and Bi (bismuth). The authors have proposed a new mechanism for the possible reactions.
文摘This paper is a result of a review through 25 papers on the synthesis of three-, four-, five-, six-, and seven-membered rings on solid support. Solid-phase organic synthesis methods that enable the rapid production of arrays of heterocycles are of critical importance to the pharmaceutical industry. The generation of heterocyclic chemistry by solid-phase synthesis will definitely accelerate the development of pharmaceutical research.
基金supported by the National Natural Science Foundation of China (21821002, 21772222, and 91956112)Chinese Academy of Sciences (XDB20000000)Science and Technology Commission of Shanghai Municipality (18JC1415600 and 20JC1417100)。
文摘Organic electrosynthesis has been widely used as an environmentally conscious alternative to conventional methods for redox reactions because it utilizes electric current as a traceless redox agent instead of chemical redox agents. Indirect electrolysis employing a redox catalyst has received tremendous attention, since it provides various advantages compared to direct electrolysis. With indirect electrolysis, overpotential of electron transfer can be avoided, which is inherently milder, thus wide functional group tolerance can be achieved. Additionally, chemoselectivity, regioselectivity, and stereoselectivity can be tuned by the redox catalysts used in indirect electrolysis. Furthermore, electrode passivation can be avoided by preventing the formation of polymer films on the electrode surface. Common redox catalysts include N-oxyl radicals, hypervalent iodine species, halides, amines, benzoquinones(such as DDQ and tetrachlorobenzoquinone), and transition metals. In recent years, great progress has been made in the field of indirect organic electrosynthesis using transition metals as redox catalysts for reaction classes including C–H functionalization, radical cyclization, and cross-coupling of aryl halides-each owing to the diverse reactivity and accessible oxidation states of transition metals. Although various reviews of organic electrosynthesis are available, there is a lack of articles that focus on recent research progress in the area of indirect electrolysis using transition metals, which is the impetus for this review.
基金supported by the National Natural Science Foundation of China (21372127, 21572104)Program for New Century Excellent Talents in University
文摘Total syntheses of terpenoids play an essential role in the development of synthetic organic chemistry and medicinal science.Chinese synthetic community has made more and more profound contribution to this field and has gradually grown into a major force in the world over the past years. In this review, we shall celebrate the achievement by surveying the recent terpenoid syntheses from China since 2010.
基金supported by National Natural Science Foundatoin of China(81222042)National Basic Research Program of China(2009CB918404,2012CB518001)
文摘Benzoxaborole,as a versatile scaffold,plays important roles in organic synthesis,molecular recognition and supramolecular chemistry.It is also a privileged structure in medicinal chemistry due to its desirable physicochemical and drug-like properties.Recently,benzoxaboroles were widely applied as antifungal,antibacterial,antiviral,anti-parasite,and anti-inflammatory agents.This review covers the properties,synthetic methods and applications of benzoxaboroles in medicinal chemistry.
基金supported by the National Natural Science Foundation of China (21302158 and 21472156)the National Basic Research Program of China (2012CB821600)
文摘Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n(M=metal;L=ligand),the corresponding organometallic complex was called metallafuran,which should be two possible isomers called a-metallafuran(metal fragment at a-carbon of original furan)and b-metallafuran(metal fragment at b-carbon of original furan).As an organometallic complex,a-metallafuran has two resonant forms:one can be viewed as carbonyl coordinated vinyl metal complex and the other can be viewed as alkoxymetal carbene.Therefore,a-metallafuran was also called chelated vinyl ketone metal complex or oxametallacyclopentadiene in the early literatures.For synthesis of metallafurans,a-metallafurans were very common and easily prepared,for example,from alkynes insertion into acyl metal complexes and so on.While there were rare examples reported for b-metallafurans.In this mini review,the synthetic chemistry of metallafuran was mainly focused on its formation mechanism.
基金the Canada Research Chair (Tier I) foundationthe E. B. Eddy Endowment Fund+1 种基金the CFI, NSERC, FQRNTthe NSF and the NSF-EPA Joint Program for a Sustainable Environment for partial support of our research over the years
文摘The sustainable development of our future represents an unorthodox challenge in sciences and technologies.The exploration of unconventional chemical reactivities that could potentially result in more sustainable chemical productions with efficient utilization of resource and inherent prevention of waste will provide the foundation for the synthetic chemistry of our future.As part of this endeavor,we have explored metal-mediated reactions in water to minimize protection-deprotection and the use of organic solvents,catalytic nucleophilic additions via C-H reactions to avoid generation and use of stoichiometric organic halides and metal in water,and Cross-Dehydrogenative-Coupling(CDC) reactions to minimize overall transformation steps.
基金supported by the National Natural Science Foundation of China (21622203, 21472147, 21272183)the Fund of Northwest University (334100036)
文摘Umpolung is a fundamental concept in organic chemistry, which provides an alternative strategy for the synthesis of target compounds which were not easily accessible by conventional methods. Herein, a mild and efficient PhI(OAc)_2-promoted umpolung acetoxylation reactions of enamides was developed for the synthesis of α-acetoxy ketones. The reaction tolerates a wide range of functional groups and affords α-acetoxy ketones in good to excellent yields. PhI(OAc)_2 serves as a source of acetoxy in the reaction.