2025年11月18日,北京大学药学院天然药物及仿生药物全国重点实验室焦宁教授团队与匹茨堡大学刘鹏教授团队在Nature Catalysis上发表题为“Late-stage conversion of carboxylic acids to nitriles with Mg and Pd cocatalysis”(镁、钯...2025年11月18日,北京大学药学院天然药物及仿生药物全国重点实验室焦宁教授团队与匹茨堡大学刘鹏教授团队在Nature Catalysis上发表题为“Late-stage conversion of carboxylic acids to nitriles with Mg and Pd cocatalysis”(镁、钯共催化的羧酸到腈的后期修饰)的原创型工作。研究团队发展了一种以钯盐、镁盐协同催化、以尿素作为氮源的羧酸高效制备腈类产物的新方法。通过双金属协同催化与焓变-熵变综合驱动,该方法温和地活化了惰性羧酸并完成腈的生成这一热力学不利的转化,实现了多官能团复杂羧酸的后期氰化修饰。展开更多
The selective conversion of CO2and NH3into valuable nitriles presents significant potential for CO2utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the ...The selective conversion of CO2and NH3into valuable nitriles presents significant potential for CO2utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO2and NH3as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.展开更多
A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO2 photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the ph...A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO2 photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO2 catalyst,which was much higher than that of pristine TiO2(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO2 promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO2 also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.展开更多
Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.M...Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.展开更多
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The cataly...A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDItol) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.展开更多
A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochlor...A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide(ZnO) as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration(〈1 min),high selectivity;and high yield(90-98%).展开更多
摘要2025年11月18日,北京大学药学院天然药物及仿生药物全国重点实验室焦宁教授团队与匹茨堡大学刘鹏教授团队在Nature Catalysis上发表题为“Late-stage conversion of carboxylic acids to nitriles with Mg and Pd cocatalysis”(镁、钯共催化的羧酸到腈的后期修饰)的原创型工作。研究团队发展了一种以钯盐、镁盐协同催化、以尿素作为氮源的羧酸高效制备腈类产物的新方法。通过双金属协同催化与焓变-熵变综合驱动,该方法温和地活化了惰性羧酸并完成腈的生成这一热力学不利的转化,实现了多官能团复杂羧酸的后期氰化修饰。
基金the National Natural Science Foundation of China(Nos.22072167,22202218)the Jiangsu Natural Science Funds for Young Scholar(No.BK20211093)is greatly appreciated.
摘要The selective conversion of CO2and NH3into valuable nitriles presents significant potential for CO2utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO2and NH3as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
基金supported by the National Key R&D Program of China(2021YFF0500703)Natural Science Foundation of Shanghai(22JC1404200)+3 种基金Program of Shanghai Academic/Technology Research Leader(20XD1404000)Natural Science Foundation of China(U22B20136,22293023)Science and Technology Major Project of Inner Mongolia(2021ZD0042)the Youth Innovation Promotion Association of CAS。
摘要A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO2 photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO2 catalyst,which was much higher than that of pristine TiO2(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO2 promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO2 also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.
摘要Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.
基金Supported by the National Natural Science Foundation of China(21476244,21406245)Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21030600)the Youth Innovation Promotion Association CAS(2016046)
摘要A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDItol) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
摘要A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide(ZnO) as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration(〈1 min),high selectivity;and high yield(90-98%).