两种水杨醛型单肟铜(Ⅱ)配合物的合成及结构研究(英文)

2种新的水杨醛型单肟配体HL1(HL1=(E)-2-{1-甲氧基亚氨基甲基}-4,6-二溴苯酚)和HL2(HL2=(E)-2-{1-乙氧基亚氨基甲基}-4-硝基苯酚)分别与一水合乙酸铜反应,合成了2个铜配合物[Cu(L1)2](1)和[Cu(L2)2](2),利用元素分析、红外光谱和紫外光谱等进行了表征,并用X-射线单晶衍射测定了其晶体结构。结果表明,配合物1、2均为单核结构,由1个CuⅡ离子和2个配体组成。中心CuⅡ离子的配位数是4。配合物1为扭曲的平面四边形,而2为规则的平面四边形。配合物1以分子间氢键形成了无限的一维链状超分子结构,而配合物2以分子间氢键和π…π作用形成了二维超分子结构。     

Construction of Chiral One-dimensional Chains via Mononuclear Chiral Precursors and Circular Dichroism Properties

One-dimensional(1D) chiral chain complexes [CuLSCu(Pydc)](2S) and [CuLRCu(Pydc)](2R)(LS=(E)-3-(((1S,2S)-2-(((E)-3-oxo-3-(4-pyridin-4-yl)phenyl)propylidene)amono)-1,2-diphenyl)imino)-1-(4-(pyridi-4-yl)phenyl)butan-1-one) and LR=(E)-3-(((1R,2R)-2-(((E)-3-oxo-3-(4-pyridin-4-yl)phenyl)propylidene)amono)-1,2-diphenyl)imino)-1-(4-(pyridi-4-yl)phenyl)butan-1-one and Pydc=2,6-pyridinedicarboxylic acid)have been synthesized vis mononuclear chiral enantiomer precursors CuLS(1S) and CuLR(1R).Their different chiral configurations of 1S,1R,2S and 2R were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses,infrared spectra(IR),powder X-ray diffraction(PXRD),thermal gravimetric analyses(TGA) and circular dichroism spectra(CD).     

Rhodiolosides A-E, monoterpene glycosides from Rhodiola rosea

Five new monoterpene glycosides, rhodiolosides A-E (1-5), were isolated from the roots of Rhodiola rosea (Crassulaceae). Their structures were elucidated as (2E,6E,4R)-4,8-dihydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranoside (1), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl alpha-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside (2), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranosyl(1-->3)-beta-D-glucopyranoside (3), (2E,4R)-4,7-dihydroxy-3,7-dimethyl-2-octenyl beta-D-glucopyranoside (4), and (2E)-7-hydroxy-3,7-dimethyl-2-octenyl alpha-L-arabinopyranosyl(1-->6)-beta-D-glucopyranoside (5), on the basis of various spectroscopic analyses and chemical degradation.     

Synthesis and Crystal Structure of a Heterometallic Chain Coordination Polymer:{[Ni_2Mn_2L_2(CH_3CH_2OH)(H_2O)]·CH_3OH·2H_2O}_n

A chain-like coordination polymer with the chemical formula of {[Ni2Mn2L2(CH3CH2OH)-(H2O)]·CH3OH·2H2O}n has been synthesized by the assembly reaction of K2NiL·H2O and Mn(OAC)2·4H2O with a 1:1 mole ratio in methanol,where OAC-=CH3COO-and H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl}imino)methyl]benzoic acid.The crystal structure was determined by single-crystal X-ray diffraction analysis.It belongs to the triclinic system,space group P1,with a=9.9464(8),b=13.4718(11),c=14.3877(12),α=87.1930(10),β=85.4280(10),γ=74.6470(10)°,V=1852.4(3)3,Z=2,Dc=1.807g/cm3,Mr=1008.03,λ(MoKα)=0.71073,μ(MoKα)=1.794 mm-1,F(000)=1032,R=0.0527 and wR=0.1284(Ⅰ2σ(Ⅰ)).The compound exhibits a chain-like structure formed by dissymmetrical tetranuclear units.     

Catalysis of oxo transfer to prochiral sulfides by oxovanadium(v) compounds that model the active center of haloperoxidases

The catalytic properties of a new class of chiral vanadium compounds--[(S,S,S)-VO(OMe)L1] (5), [(S,S)-VO(OMe)L2] (6), [(S,S)-VO(OMe)L3] (7), and [(R,R,R)-VO(OMe)L4] (8), as well as the system VO(OiPr)(3)/(R,R,R)-H(2)L4 [H(2)L1=(S,S)-bis(2-hydroxypropyl)-(S)-1-phenylethylamine, 1; H(2)L2=(S,S)-bis(2-hydroxypropyl)benzylamine, 2; H(2)L3=(S,S)-bis(2-hydroxypropyl)isopropylamine), 3; (H(2)L4)=(R,R)-bis(2-phenylethanol)-(R)-1-phenylethylamine, 4]--in the asymmetric oxidation of prochiral sulfides by organic hydroperoxides have been investigated. Particular attention has been paid to the factors that guide the discrimination between the two prochiral faces of the sulfides (methyl p-tolyl sulfide and benzyl phenyl sulfide), to steric implications stemming from the oxidant (cumyl hydroperoxide and tert-butyl hydroperoxide), and to the specific complex used. As an example, (S)-methyl p-tolyl sulfoxide was obtained in a 31 % enantiomeric excess by use of cumyl hydroperoxide as oxidant and complex 5 as the catalyst, after 150 min at 0 degrees C and with 100 % conversion of the sulfide. The crystal and molecular structures of 5 and 6 reveal the close relationship between these complexes and the active center of vanadate-dependent haloperoxidases: the vanadium is in a slightly distorted trigonal-bipyramidal environment with the nitrogen and the methoxy group in the axial positions, and the oxo and alkoxide functions of L2 and L3 are the plane. The presence and equilibrium situation of isomers of the catalysts in solution has been investigated by (51)V EXSY and variable-temperature multinuclear NMR spectroscopy. An intermediately formed peroxo (ROO(-)) vanadium complex was detected by (51)V NMR spectroscopy.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. V

Nine novel prenyl-dihydrofurocoumarin-type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4-methyl-5- (4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadien-6-onyl]-furo-[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E)-pentenyl]-furo[3,2-c]coumarin, were isolated from the roots of Ferula ferulaeoides [corrected]. The structures were established by comprehensive spectral analysis. The biosynthetic pathway leading to these prenyl-furocoumarin-type sesquiterpenoids is proposed based on their structures.     

Studies on the constituents of Broussonetia species. VII. Four new pyrrolidine alkaloids, broussonetines M, O, P, and Q, as inhibitors of glycosidase, from Broussonetia kazinoki SIEB

Four new pyrrolidine alkaloids, broussonetines M, O, P, and Q, were isolated from the branches of Broussonetia kazinoki SIEB, (Moraceae). Broussonetines M, O, P, and Q were formulated as (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(10S)-10,13-dihydroxy-tri decyl]pyrrolidine (1), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(E)9-oxo-13-hydroxy-3- tridecenyl]pyrrolidine (2), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(E)10-oxo-13-hydroxy-3-++ +tridecenyl]pyrrolidine (3), and (2R,3S,4R,5R)-2-hydroxymethyl-3-hydroxy-4-(beta-D-glucopyranosyloxy++ +)-5-[10-oxo-13-(beta-D-glucopyranosyloxy)tridecyl]pyrrolidine (4) respectively, by spectroscopic and chemical methods. 1-4 inhibited beta-glucosidase, beta-galactosidase and beta-mannosidase.     

The reaction of (4R,5R)- and (4S,5S)-4,5-epoxy-2(E)-hexenoates and secondary amines.

A reaction of methyl (4R,5R)-4,5-epoxy-2(E)-hexenoate 1 with N-benzylmethylamine gave a diastereomerically pure methyl (4R,5R)-4,5-epoxy-(3S)-N-benzylmethylamino hexanoate 6 and methyl (4S,5R)-4-N-benzyl-methylamino-5-hydroxy-2(E)-hexenoate 7. The former was chemoenzymatically converted to (-)-osmundalactone 11, which is an aglycone of osmundalin. On the other hand, the directly conjugated addition of dimethylamine to methyl (4S,5S)-4,5-epoxy-2(E)-hexenoate 1 followed by treatment with MeOH at 40 degrees C exclusively provided methyl (4R,5S)-4-dimethylamino-5-hydroxy-2(E)-hexenoate 16, which was converted into L-(-)-forosamine 18.     

New sesquiterpenes from Ferula ferulaeoides (Steud.) Korovin. VI. Isolation and identification of three new dihydrofuro[2,3-b]chromones

Three novel 2-prenyl-dihydrofurochromone-type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]-furo[2,3-b]chromone, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E),7-pentenyl]-furo[2,3-b]chromone, and 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-2-[4-methyl-5-(4-methyl-2-furyl)-3(E),7-pentenyl]-furo[2,3-b]chromone, were isolated from the roots of Ferula ferulaeoides. The structures were established by comprehensive spectral analysis. The biosynthetic pathway leading to these 2-prenyl-dihydrofurochromone-type sesquiterpenoids is proposed based on their structures.     

Three new diarylheptanoids and their antioxidant property

Three new diarylheptanoids,i.e.,sodium(5S,2E)-1,7-bis(4-hydroxyphenyl)-1-hydroxy-2-hepten-5-sulfonate(1), sodium(5R,2E)-1,7-bis(4-hydroxyphenyl)-1-hydroxy-2-hepten-5-sulfonate (2) and 3,5-diacetoxy-1-(3-methoxy-4,5-dihydroxy- phenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane (3) were isolated from the rhizomes of Zingiber officinale.The structures of the new compounds were elucidated on the basis of spectroscopic methods.The antioxidant activities of 3 were assayed by in vitro models involving DPPH free radicals and superoxide anion radicals.     

Sesquiterpenoid derivatives from Ferula ferulaeoides [correction of ferulioides]. IV

Four novel prenyl-furocoumarin type sesquiterpenoid derivatives, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2R*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo[3,2-c]coumarin, 2,3-dihydro-7-hydroxy-2S*,3R*-dimethyl-3-[4-methyl-5-(4-methyl-2-furyl)- 3(E)-pentenyl]-furo[3,2-c]coumarin, and 2,3-dihydro-7-methoxy-2S*,3R*-dimethyl-3-[4,8-dimethyl-3(E),7-nonadie nyl]-furo]3,2-c]coumarin were isolated from the roots of Ferula ferulaeoides [corrected]. Their structures were established by detailed spectral analysis and the biosynthetic pathway leading to these prenyl-furocoumarin type sesquiterpenoids is proposed based on these structures.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.     

稀土-荧光素双重荧光响应pH探针分子的合成与荧光性质研究

将含有8-氨基喹啉与荧光素衍生物缩合的席夫碱QZ1与铕髥的TTA(噻吩基三氟乙酰丙酮)化合物作为基本原料合成了新的铕髥-荧光素化合物Eu-QZ1,并对其进行了光谱表征。化合物Eu-QZ1在470 nm光的激发下产生荧光素的特征绿色荧光(530 nm)。在从碱到酸(pH从9.0到6.0)滴定过程中该荧光的强度增强了接近5倍,其pKa值计算为7.30。在370 nm光的激发下,Eu-QZ1发射稀土铕髥离子的特征红色荧光(主峰位于612 nm)。在从酸到碱(pH从5.5到8.5)滴定过程中,该荧光的强度增强了接近10倍,其pKa值计算为7.39。这些结果表明Eu-QZ1是1个高灵敏度双荧光响应的pH探针。细胞试验表明Eu-QZ1具有良好的细胞通透性,能够在红光和绿光两个位置标记海拉细胞中的pH范围。     

New cytotoxic butanolides from Lindera obtusiloba BLUME

Three new butanolides, 2-(1-methoxy-11-dodecenyl)-penta-2,4-dien-4-olide (1), (2Z,3S,4S)-2-(11-dodecenylidene)-3-hydroxy-4-methylbutano lide (2) and (2E,3R,4R)-2-(11-dodecenylidene)-3-hydroxy-4-methoxy-4-methylbu tanolide (3), were isolated from the stems of Lindera obtusiloba BLUME. Their chemical structures were assigned by spectroscopic evidence. They exhibited cytotoxicity against cultured human tumor cell lines with their ED50 values ranging from 3.19 to 14.63 microg/ml.     

抗体酶催化Oxy-Cope重排反应的研究

经七步反应合成了Oxy-Cope重排反应的过渡态类似物-2-对羧丙氧基苯基环己醇(3),并以此为半抗原联接载体蛋白BSA制成抗原后免疫动物,从动物血清中分离纯化得到多克隆抗体。在200mmol/L的MES(4-吗啉乙磺酸)和200mmol/L的NaCl缓冲液中(pH=6.0),底物和抗体的摩尔比为100:1及37℃条件下,该抗体能催化3-对甲氧苯基-4-羟基-1,5-已二烯(1)重排生成6-对甲氧苯基-5-烯-已醛(2),ν~m~a~x=15μmol/L·min,K~M=1025μmol/L,K~c~a~t~.=10min^-^1.     

Studies on the constituents of Broussonetia species VIII. Four new pyrrolidine alkaloids, broussonetines R, S, T, and V and a new pyrroline alkaloid, broussonetine U, from Broussonetia kazinoki Sieb

Four new pyrrolidine alkaloids, broussonetines R, S, T, and V and a new pyrroline alkaloid, broussonetine U were isolated from the branches of Broussonetia kazinoki SIEB. (Moraceae) in low yield. Broussonetines R, S and T were formulated as (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(1R)-1-hydroxy-3-[6-(4-hydroxybutyl)-cyclohexy-2-on-1(6)-enyllpropyl] pyrrolidine (1), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(1R,10S)-1,10,13-trihydroxytridecyl] pyrrolidine (2), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(1R,5S)-1,5, 13-trihydroxy-10-oxo-tridecyl] pyrrolidine (3). And broussonetines U and V were proposed to be (2S,3S,4S)-2-hydroxymethyl-3, 4-dihydroxy-5-(9-oxo-13-hydroxytridecyl)-5-pyrroline (4), (2R,3S,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(E)-9-oxo-13-hydroxy-3-tridecenyl] pyrrolidine (5), respectively, by spectroscopic and chemical methods.     

Cerebrosides from the roots of Serratula chinensis

A new cerebroside, 1-O-beta-D-glucopyranosyl-(2S,3R,8E)-2-[(2'R)-2-hydroxy- palmitoylamino]-8-octadecene-1,3-diol, along with aralia cerebroside and 1-O-beta-D- glucopyranosyl-(2S,3S,4R,8E)-2-[(2'R)-2-hydroxybehenoylamino]-8-octadecene-1,3,4-triol were isolated from the roots of Serratula chinensis S. Moore. The structure of the new cerebroside was established by spectroscopic and chemical means. Occurrence of cerebrosides in Serratula is reported here for the first time.     

单核铜配合物Cu(C_(16)H_(13)N_2OS_2)_2的合成、晶体结构和生物活性(英文)

A planar copper complex Cu(L)2,HL=(E)-benzyl-2-(4-formylbenzylidene)-Hydrazinecarbodithioate,has been prepared via the template effect of copper ion. Crystal structure of the complex was determined by X-ray singlecrystal diffraction analysis. The crystal data for this complex:Orthorhombic,space group Pbcn,a=2.250 0(14) nm,b=1.660 0(11) nm,c=0.830 4(5) nm,V=3.102(3) nm3,Z=4,μ=1.011 mm-1,Dc=1.478 g·cm-3,F(000)=1 420,R1= 0.050 1,wR2=0.087 2 (observed reflections with I2σ(I)) and R1=0.129 1,wR2=0.100 9 (all reflections) GOF= 1.011. In the compound,Cu(Ⅱ) atom is four-coordinated with two N atoms and two S atoms from two bidentate ligands and located in the inversion center. The preliminary bioassay indicates that the complex exhibits distinct antitumor activity.     

Total synthesis of (S)-(+)-curcudiol, and (S)-(+)- and (R)-(-)-curcuphenol.

A highly enantioselective synthesis of the versatile chiral synthons possessing one stereogenic center, (S)- and (R)-4-aryl-5-hydroxy-(2E)-pentenoate (3) was achieved based on the enzymatic reaction of (+/-)-3 with commercially available lipases MY-30 or OF-360 from Candida rugosa. Application of (S)-3 and (R)-3 to the total syntheses of(S)-curcuphenol (1), (S)-curcudiol (2), and (R)-curcuphenol (1), respectively, is described.     

Synthesis, structures and catalytic properties of iron(III) complexes with asymmetric N-capped tripodal NO3 ligands and a pentadentate N2O3 ligand

A new family of N-capped tripodal NO(3) proligands N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-N-(2'-hydroxy-5'-R-phenyl)amine [H(3)(L(n))] [when R= Me, n = 1; R= (t)Bu, n = 2; R = Cl, n = 3] with different substituents in one of the aryl rings and N,N-bis(2-hydroxy-3-tert-butylbenzyl)-N-(2'-hydroxy-5'-methylphenyl)amine [H(3)(L(4))] were synthesised. The preparation of a new pentadentate proligand N-methyl-N,N',N'-tris(2-hydroxy-3,5-di-tert-butylbenzyl)ethane-1,2-diamine [H(3)(L(5))] with an N(2)O(3) donor set is also reported. Reaction of the proligands [H(3)(L(n))] (n = 1-4) with iron(iii) chloride in the presence of base (triethylamine) and 1-methylimidazole (1-Meim) as co-ligand led to the formation of iron complexes of the type [Fe(L(n))(1-Meim)] (n = 1-4) () respectively, while treatment of the trilithium salt of [H(3)(L(5))] with iron(iii) chloride afforded [Fe(L(5))] (). All complexes were structurally characterised by X-ray crystallography. In complexes , the ligands form five- and six-membered chelate rings with the iron centres which have distorted trigonal bipyramidal geometry with an N(2)O(3) coordination environment. Complex adopts a similar distorted trigonal bipyramidal geometry also with N(2)O(3) coordination around the iron centre. The catalytic activity of these iron complexes towards epoxidation of styrene was examined.