Various amino acid esters were reacted with different isothiocyanates in alkaline Al2O3 at room temperature for 1 h affording thiohydantoins in moderate to excellent yields.
Main observation and conclusion An HPLC-UV-guided separation was performed and four pairs of unprecedented macathiohydantoin dimers,lepithiohydimerins A—D(1—4)bearing a rare disulfide bond were isolated from the tub...Main observation and conclusion An HPLC-UV-guided separation was performed and four pairs of unprecedented macathiohydantoin dimers,lepithiohydimerins A—D(1—4)bearing a rare disulfide bond were isolated from the tubers of Maca.Their structures were unambiguously confirmed by NMR spectroscopic,X-ray crystallographic and electronic circular dichroism(ECD)analyses.At the concentration of 20μmol/L,compounds 2-1,2-2,and 4-1 increased the viability of PC12 cells with the cell viability at(72.06±1.14)%,(72.64±1.49)%,and(70.93±1.22)%,respectively.Furthermore,the serial concentration experiment showed that they can protect PC12 cells in a dose-dependent manner.展开更多
对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2...对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。展开更多
By the reaction of Co2(CO)8 with 2-thiohydantoins S-CNHC(O)C(R1) (R2)NC(O)R3(HL), a new cluster with formula Co3(CO)7 (μ3-S) (μ3, η2-S CNC(O)C(CH3)2N C(O)CH3 hasbeen prepared. The cluster has been characterized by ...By the reaction of Co2(CO)8 with 2-thiohydantoins S-CNHC(O)C(R1) (R2)NC(O)R3(HL), a new cluster with formula Co3(CO)7 (μ3-S) (μ3, η2-S CNC(O)C(CH3)2N C(O)CH3 hasbeen prepared. The cluster has been characterized by elemental analysis, IR, 1H NMR and MS spectroscopy.The crystal structure of the cluster has been determined by X-ray single crystal diffraction method.The crystal of the cluster is triclinic, belonging to space group P1 and the cell parameters are as follows: a=8.456 (3), b=11.534(3), c= l1.990(4)A, α=107.36(3), β=108.44(5), γ=90.,18(3)°. Thestructural analysis shows that this molecule contains a tetrahedral cluster framword Co3S and2-thiohydantoin as bridging ligands links up with two cobalt atoms of the framwork by S- andN-atom thus -a five member ring of Co2 NCS has been formed.展开更多
Maca(Lepidium meyenii Walp.),a famous food supplement,has drawn an unprecedented international interest over the last two decades.It was assumed that glucosinolates,macamides,macaenes,and alkaloids are the main bioact...Maca(Lepidium meyenii Walp.),a famous food supplement,has drawn an unprecedented international interest over the last two decades.It was assumed that glucosinolates,macamides,macaenes,and alkaloids are the main bioactive components of Maca before.Recently,a series of novel thiohydantoins which generally exhibit a variety of activities have been isolated from Maca.This review focuses on the progress on the main bioactive components of Maca and their biosynthetic pathway,which indicates that macamides,thiohydantoins,and some alkaloids may originate from glucosinolates.Interestingly,thiohydantoins from Maca are the first type of thiohydantoin derivatives to be found from a natural source and may contribute to some significant effects of Maca.展开更多
基金National Natural Science Foundation of China(Grant No.20972005)
文摘Various amino acid esters were reacted with different isothiocyanates in alkaline Al2O3 at room temperature for 1 h affording thiohydantoins in moderate to excellent yields.
基金supported by grants from the National Natural Science Foundation of China(No.31872675)Fund of State Key Laboratory of Phytochemistry and Plant Resources in West China(P2020-KF02).
文摘Main observation and conclusion An HPLC-UV-guided separation was performed and four pairs of unprecedented macathiohydantoin dimers,lepithiohydimerins A—D(1—4)bearing a rare disulfide bond were isolated from the tubers of Maca.Their structures were unambiguously confirmed by NMR spectroscopic,X-ray crystallographic and electronic circular dichroism(ECD)analyses.At the concentration of 20μmol/L,compounds 2-1,2-2,and 4-1 increased the viability of PC12 cells with the cell viability at(72.06±1.14)%,(72.64±1.49)%,and(70.93±1.22)%,respectively.Furthermore,the serial concentration experiment showed that they can protect PC12 cells in a dose-dependent manner.
文摘对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。
文摘By the reaction of Co2(CO)8 with 2-thiohydantoins S-CNHC(O)C(R1) (R2)NC(O)R3(HL), a new cluster with formula Co3(CO)7 (μ3-S) (μ3, η2-S CNC(O)C(CH3)2N C(O)CH3 hasbeen prepared. The cluster has been characterized by elemental analysis, IR, 1H NMR and MS spectroscopy.The crystal structure of the cluster has been determined by X-ray single crystal diffraction method.The crystal of the cluster is triclinic, belonging to space group P1 and the cell parameters are as follows: a=8.456 (3), b=11.534(3), c= l1.990(4)A, α=107.36(3), β=108.44(5), γ=90.,18(3)°. Thestructural analysis shows that this molecule contains a tetrahedral cluster framword Co3S and2-thiohydantoin as bridging ligands links up with two cobalt atoms of the framwork by S- andN-atom thus -a five member ring of Co2 NCS has been formed.
基金This research work was financially supported by NSFC project and YiKe R&D Project(KIB-20140708Q)as well as Foundation of Key Laboratory of Tobacco Chemistry of Yunnan Province(KCFZ-2017-1096)Foundation of State Key Laboratory of Phytochemistry and Plant Resources in West China(P2010-ZZ14).
文摘Maca(Lepidium meyenii Walp.),a famous food supplement,has drawn an unprecedented international interest over the last two decades.It was assumed that glucosinolates,macamides,macaenes,and alkaloids are the main bioactive components of Maca before.Recently,a series of novel thiohydantoins which generally exhibit a variety of activities have been isolated from Maca.This review focuses on the progress on the main bioactive components of Maca and their biosynthetic pathway,which indicates that macamides,thiohydantoins,and some alkaloids may originate from glucosinolates.Interestingly,thiohydantoins from Maca are the first type of thiohydantoin derivatives to be found from a natural source and may contribute to some significant effects of Maca.
