以1-（3-羧苯基）-5-甲基-1氢-1，2，3-三唑-4-羧酸为配体构筑的两个配合物的合成、晶体结构及性质

1-（3-羧苯基）-5-甲基-1氢-1,2,3-三唑-4-羧酸为配体与锰金属盐、锌金属盐在水热合成法得到2个配位聚合物：{Mn（cpmtc）₂（H₂O）₂}_n（1）,{Zn（cpmtc）₃（H₂O）}_n（2）。通过单晶衍射仪测得这2个晶体结构,配位聚合物1为单斜晶系,P2₁/c空间群;a=1.18352（19）nm,b=1.19801（19）nm,c=0.99876（16）nm,β=113.201°。配位聚合物2属于单斜晶系,P2₁/c空间群;a=1.0233（3）nm,b=1.1720（4）nm,c=1.0233（3）nm,β=92.8700°。除此之外,这2个配位聚合物通过红外和荧光进行表征。     

二核双席夫碱铜(Ⅱ)配合物的合成、晶体结构及抗菌活性研究

合成了一对结构类似的双核铜配合物,[CuL¹]₂（1）和[CuL²]₂（2）,其中L¹是双席夫碱配体N,N’-二（5-氟水杨基）-1,3-丙二胺（H₂L¹）的二价阴离子,L²是N,N’-二（5-氟水杨基）-1,2-乙二胺（H₂L²）的二价阴离子,通过元素分析、红外光谱以及单晶X-射线衍射表征了它们的结构。配合物1以单斜晶系P2₁/c空间群结晶,其晶体学参数a=1.3488（1）nm,b=0.6814（1）nm,c=1.7087（1）nm,β=108.903（3）°,V=1.4857（2）nm³,Z=4,R₁=0.0480,wR₂=0.1141,Goof=1.115。配合物2以单斜晶系C2/c空间群结晶,其晶体学参数a=2.7568（2）nm,b=0.7036（1）nm,c=1.4547（1）nm,β=94.758（2）°,V=2.8118（5）nm³,Z=4,R₁=0.0472,wR₂=0.1139,Goof=1.094。X-射线分析表明2个化合物都是中心对称的双核配合物,其中Cu原子都是四方椎配位构型。通过MTT法研究了这2个配合物的抗细菌（枯草芽孢杆菌,金黄色葡萄球菌,大肠杆菌和荧光假单胞菌）和抗真菌（白假丝酵母菌和黑曲霉菌）活性。     

ApoCopC与汞（II）结合性质的光谱研究

在室温, pH 7.4, 10 mmol•L^-1Hepes（N-2-hydroxyethylpiperazine-N’-2-ethane-sulfonic acid）缓冲溶液条件下，通过紫外光谱法研究了apoCopC与汞（II）的结合性质。结果表明apoCopC的N，C- 端均可结合汞（II），且测得条件结合常数分别为K_n=(6.79 ± 1.12)´10⁶ mol^-1•L和K_c= (3.06±0.05)´10⁵ mol^-1•L。在pH 7.4，50 mmol·L^-1Hepes缓冲溶液条件下，用荧光光谱法研究了apoCopC的脲变性性质。结果表明汞（II）的结合对蛋白结构的维系具有稳定作用，并测得Hg_N²⁺-CoC-Hg_c²⁺ 和apoCopC的稳定吉布斯自由能（ΔG_D^H2O）分别为14.69±0.85 kJ•mol^-1和 16.66±0.55 kJ•mol^-1。     

以2,2’-联吡啶-4,4’-二甲酸和2-甲基吡嗪[3,2-f：2’,3’-h]喹喔啉为配体的三维锰（Ⅱ）配位聚合物的合成、晶体结构和荧光性质

采用水热法合成了一个锰的配合物[Mn（bpydc）（Medpq）]_n（1）（H₂bpydc=2,2’-联吡啶-4,4’-二甲酸,Medpq=2-甲基吡嗪[3,2-f：2’,3’-h]喹喔啉）,并利用元素分析、红外光谱、紫外可见光谱、热分析和X-射线单晶衍射对其结构进行了表征。单晶结构分析表明配合物1属于正交晶系,Cc空间群,晶胞参数a=2.0316（4）nm,b=1.5645（3）nm,c=0.71926（14）nm,β=103.97（3）,V=2.2185（8）nm³,Z=4。配合物1是一个锰(Ⅱ)离子经由bpydc^2-连接形成的三维网络结构。配合物1的固体荧光光谱表明它具有很强的荧光性。应用Gaussian03W程序,在HF/LANL2DZ水平上对标题化合物的自然键轨道（NBO）进行了分析,结果表明Mn(Ⅱ)与配位原子间的价键类型都属于共价键范畴。     

氮杂环卡宾羰基氯钌配合物的合成、晶体结构及催化性质

合成了2个N-杂环卡宾钌配合物[RuCl₂（L1）（CO）]（1）,L1=（2,6-二（甲基咪唑-2-鎓盐）吡啶）和[RuCl₂（L2）（CO）]（2）,L2=（2,6-二（正丁基-2-鎓盐）吡啶）,并通过元素分析、红外光谱、核磁共振氢谱和核磁共振碳谱对它们的结构进行了表征,X-射线单晶衍射测定了配合物2的分子结构,结果表明配合物2属单斜晶系,C2/c空间群,a=1.8148（4）nm,b=1.1292（3）nm,c=1.1196（2）nm,β=108.862（3）°,且中心Ru（Ⅱ）离子是六配位,同时研究了配合物1和2在Suzuki-Miyaura偶联反应中的催化性质。     

[Co(ptma)(amp)Cl]2+体系的一反式经式异构体(m3[ZnCl4]·0.5H2O)的晶体结构

在合成[Co(bpma)(tn)Cl]²⁺体系配合物的实验中,得到[Co(ptma)(amp)Cl]²⁺体系的一反式(ptma中仲胺上的氢相对于Cl)经式异构体(m3[ZnCl₄]·0.5H₂O),其中bpma=N,N′-二(2-吡啶基甲基)胺,tn=1,3丙二胺,ptma=N-(2-吡啶基甲基)丙二胺,amp=2-(氨基甲基)吡啶。此配合物异构体构型选择性形成的原因可能主要是其结构中配体间C-H…π相互作用使之更稳定的结果。利用单晶X-射线衍射法测定的晶体学参数:单斜晶系,空间群C2/c,a=1.55978(19)nm,b=1.33324(16)nm,c=2.2077(3)nm,β=94.832(3)°,V=4.5748(10)nm³,D_c=1.696g·cm^-3,Z=8,F₀₀₀=2360,μ(MoKα)=23.72cm^-1,R=0.0475,R_w=0.1204。配合物离子中Co³⁺为六配位。晶胞中含8个配合物阳离子,8个[ZnCl₄]^2-阴离子及4个水分子,对映体的比例为1∶1。     

2，9-二甲基菲咯啉CuⅠ和Cu(Ⅱ)配合物的合成、晶体结构和性质

以二水合氯化铜,2,9-二甲基菲咯啉（dmphen）和硫氰酸铵为原料,通过沉淀反应和N,N-二甲基甲酰胺（DMF）重结晶得到了2个新型配合物[CuⅠ（dmphen）（SCN）]_n（1）和[Cu(Ⅱ)（dmphen）（DMF）（NCS）₂]（2）,并采用元素分析、红外光谱、紫外可见光谱、X射线单晶衍射、热重分析及荧光光谱对其进行了表征。结果表明：1属单斜晶系,P2₁/n空间群,晶胞参数为a=1.211 1（4）nm,b=0.826 2（2）nm,c=1.367 5（4）nm,β=96.502（5）°,V=1.359 5（7）nm³,Z=4;该配合物通过硫氰酸根的桥联作用形成了一维Z链结构。2为三斜晶系,P1空间群,晶胞参数a=0.943 6（2）nm,b=1.010 9（2）nm,c=1.219 0（3）nm,α=95.628（4）°,β=103.114（4）°,γ=107.087（4）°,V=1.065 4（4）nm³,Z=2;2通过C-H…S氢键和π-π堆积构筑成一个超分子网络结构。热重和荧光分析表明：1比2具有更高的热稳定性,且1在603 nm处有最强荧光发射强度。     

基于大环醚和三价卤化铋阴离子的超分子杂化化合物：合成、结构及性质

基于大环自组装和多卤阴离子合成了有机-无机杂化超分子化合物,[（1,4-PMNH₃）·（18-crown-6）]·[（H₃O）·（18-crown-6）]₂·[（H₂O）·（18-crown-6）]·（18-crown-6）·（Bi₂Cl₉）（1）。化合物属正交晶系,Pca2₁空间群,a=2.4830（3）nm,b=1.1618（3）nm,c=3.3161（2）nm,V=9.566（2）nm³。并通过其红外光谱、粉末衍射、热重分析和单晶结构分析对化合物进行了充分表征。在转子定子型的超分子化合物1中,大环超分子阳离子和（Bi₂Cl₉）^3-阴离子交错堆积形成包合物结构。并在室温下对其固体荧光性质进行测试表征。通过DSC对其热稳定性进行了详细分析。     

两个由醋酸根和含吡啶基配体构筑的Zn(II)配聚物的合成、晶体结构及其荧光性质

以醋酸锌、异烟肼（INH）、2-氨基吡啶（2-APy）为原料在N,N-二甲基甲酰胺（DMF）溶液中合成了2个Zn（Ⅱ）配位聚合物[Zn（CH₃COO）₂（INH）]_n（1）,[Zn（CH₃COO）₂（2-APy）]_n（2）,用红外光谱、元素分析、粉末X射线衍射、X射线单晶衍射对配合物进行了表征。晶体结构测试表明,配聚物1属单斜晶系,空间群P2₁/c,晶胞参数：a=0.914 44（17）nm,b=0.161 86（3）nm,c=0.871 75（16）nm,β=96.181（3）°,V=1.282 8（4）nm³,Z=4;配聚物为2D层状结构,该层状结构通过氢键弱相互作用,进一步形成3D超分子结构。配聚物2属三斜晶系,空间群P1,晶胞参数：a=0.747 0（4）nm,b=0.814 5（5）nm,c=1.895 7（11）nm,α=88.276（8）°,β=86.202（8）°,γ=84.334（8）°,V=1.144 9（11）nm³,Z=2;配聚物2为一维zig-zag链状结构。室温固态荧光测试显示,配聚物1、2分别在最大波长382.6和367.5 nm处具有较强的荧光发射。     

两个由醋酸根和含吡啶基配体构筑的Zn(Ⅱ)配聚物的合成、晶体结构及其荧光性质

以醋酸锌、异烟肼（INH）、2-氨基吡啶（2-APy）为原料在N,N-二甲基甲酰胺（DMF）溶液中合成了2个Zn（Ⅱ）配位聚合物[Zn（CH₃COO）₂（INH）]_n（1）,[Zn（CH₃COO）₂（2-APy）]_n（2）,用红外光谱、元素分析、粉末X射线衍射、X射线单晶衍射对配合物进行了表征。晶体结构测试表明,配聚物1属单斜晶系,空间群P2₁/c,晶胞参数：a=0.914 44（17）nm,b=0.161 86（3）nm,c=0.871 75（16）nm,β=96.181（3）°,V=1.282 8（4）nm³,Z=4;配聚物为2D层状结构,该层状结构通过氢键弱相互作用,进一步形成3D超分子结构。配聚物2属三斜晶系,空间群P1,晶胞参数：a=0.747 0（4）nm,b=0.814 5（5）nm,c=1.895 7（11）nm,α=88.276（8）°,β=86.202（8）°,γ=84.334（8）°,V=1.144 9（11）nm³,Z=2;配聚物2为一维zig-zag链状结构。室温固态荧光测试显示,配聚物1、2分别在最大波长382.6和367.5 nm处具有较强的荧光发射。     

基于杯[4]芳烃和S-联萘酚的荧光传感器的合成及其对N-Boc保护谷氨酸阴离子的对应选择性识别性能研究

合成了一种基于杯[4]芳烃和S-联萘酚单元的新型手性大环受体4,并用荧光光谱和核磁氢谱研究了该受体与阴离子的键合性质。非线性曲线拟合结果表明受体4与N-Boc保护L-和D-谷氨酸阴离子都能通过多重氢键形成1:1的络合物,而且对N-Boc保护谷氨酸阴离子对映体显示了较好的对应选择性识别性能（Kass(L) / Kass(D) = 4.65）。不同的荧光响应表明受体4可以用作N-Boc保护谷氨酸阴离子的对应选择性的荧光化学传感器。     

基于(R)-1,1’-联萘硫脲的手性荧光受体: 合成与手性识别

Two chiral fluorescent receptors 1 and 2 based on (R)-1,1‘-binaphthylene-2,2‘-bisthiourea were synthesized, and their chiral recognition properties for enantiomeric mandelate anions were studied by fluorescence spectra and molecular modeling. Addition of the L- and D-mandelate anions caused considerable fluorescent increases in the fluorescent intensity of the host solution. The L-enantiomer can enhance the fluorescence intensity of 1 much more than the D-enantiomer can do, and 1 shows a better enantioselective recognition ability than 2.     

Racemic and chiral 1‐[N‐(chloro­acetyl)carbamoylamino]‐2,3‐dihydro‐1H‐inden‐2‐yl chloroacetate

In the racemic crystals of (1S,2R)‐ or (1R,2S)‐1‐[N‐(chloro­acetyl)­carbamoyl­amino]‐2,3‐di­hydro‐1H‐inden‐2‐yl chloro­acetate, C₁₄H₁₄Cl₂N₂O₄, (I), the enantiomeric mol­ecules form a dimeric structure via the N—H?O cyclic hydrogen bond of the carbamoyl moieties. In the chiral crystals of (—)‐(1S,2R)‐1‐[N‐(chloro­acetyl)­carbamoyl­amino]‐2,3‐di­hydro‐1H‐inden‐2‐yl chloro­acetate, C₁₄H₁₄Cl₂N₂O₄, (II), the N—­H?O intermolecular hydrogen bond forms a zigzag chain around the twofold screw axis. The melting points and calculated densities of (I) and (II) are 446 and 396 K, and 1.481 and 1.445 Mg m^?3, respectively.     

3‐Fluoro‐N‐methyl‐D‐aspartic acid (3F‐NMDA) Stereoisomers as Conformational Probes for Exploring Agonist Binding at NMDA Receptors

N‐Methyl‐D ‐aspartate (NMDA) is the prototypical agonist of the NMDA receptor subtype of ionotropic glutamate receptors. Stereogenic placement of a C? F bond at the 3‐position of (S)‐NMDA generates either the (2S,3S)‐ or (2S,3R)‐ diastereoisomers of 3F‐NMDA. The individual diastereoisomers were prepared by synthesis in enantiomerically pure forms and it was found that (2S,3S)‐3F‐NMDA is an agonist with a comparable potency to NMDA itself, whereas the (2S,3R)‐diastereoisomer has negligible potency. The difference in potency of these stereoisomers is attributed to a preference of the C? F bond (2S,3S)‐3F‐NMDA to adopt a gauche conformation to the C? N⁺ bond in the binding conformation, whereas the (2S,3R)‐3F‐NMDA forces these bonds anti, losing electrostatic stabilisation, to achieve the required binding conformation. These observations illustrate the utility of stereoselective fluorination in influencing the molecular conformation of β‐fluorinated amino acids and thus probing the active conformations of bioactive compounds at receptors.     

Asymmetric anionic polymerization of N‐1‐naphthylmaleimide with chiral ligand‐organometal complexes in toluene

Asymmetric anionic homopolymerizations of N‐1‐naphthylmaleimide (1‐NMI) were performed with chiral ligand/organometal complexes to form optically active polymers. Poly(1‐NMI)s obtained with methylene‐bridged bisoxazoline derivatives (Rbox)‐diethylzinc (Et₂Zn) complexes showed high specific optical rotations ([α]) from +152.3 to +191.4°. Circular dichroism spectra of the polymers exhibited a split Cotton effect in the UV absorption‐band region. According to the exciton chirality method, the absolute configuration of the polymer main chain was determined according to the following method: (+)‐poly[N‐substituted maleimides (RMI)] main chains can contain more (S,S)‐ than (R,R)‐configurations. (?)‐Poly(RMI) main chains can contain more (R,R)‐ than (S,S)‐configurations. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3556–3565, 2001     

Synthesis of optically active af‐(1‐Ethyl‐3‐methylhexahydro‐1,3‐diazin‐5‐yl)‐ and N‐(1‐Ethyl‐5‐methyloctahydro‐1,5‐diazocin‐3‐yl)pyridine‐3‐carboxamides

As part of the structure‐activity relationship of the dopamine D₂ and serotonin 5‐HT₃ receptors antagonist 1, which is a clinical candidate with a broad antiemetic activity, the synthesis and dopamine D₂ and serotonin 5‐HT₃ receptors binding affinity of (R)‐5‐bromo‐N‐(1‐ethyl‐3‐methylhexahydro‐1,3‐diazin‐5‐yl)‐ and (R)‐5‐bromo‐N‐(1‐ethyl‐5‐methyloctahydro‐1,5‐diazocin‐3‐yl)‐2‐methoxy‐6‐methylaminopyridine‐3‐carboxam‐ides ( 2 and 3 ) are described. Treatment of 1‐ethyl‐2‐(p‐toluenesulfonyl)amino‐3‐methylaminopropane dihy‐drochloride ( 4a ) with paraformaldehyde and successive deprotection gave the 5‐aminohexahydro‐1,3‐diazine 6 in excellent yield. 3‐Amino‐1‐ethyl‐5‐methyloctahydro‐1,5‐diazocine ( 15 ) was prepared from 2‐(benzyloxycarbonyl)amino‐3‐[[N‐(tert‐butoxycarbonyl)‐N‐methyl]amino]‐1‐ethylaminopropane ( 9 ) through the intramolecular amidation of (R)‐3‐[N‐[(2‐benzyloxycarbonylamino‐3‐methylamino)propyl]‐N‐ethyl]aminopropionic acid trifluoroacetate ( 12 ), followed by lithium aluminum hydride reduction of the resulting 6‐oxo‐1‐ethyl‐5‐methyloctahydrodiazocine ( 13 ) in 41% yield. Reaction of the amines 6 and 15 with 5‐bromo‐2‐methoxy‐6‐methylaminopyridine‐3‐carboxylic acid furnished the desired 2 and 3 , which showed much less potent affinity for dopamine D₂ receptors than 1 .     

Model Construction for the A–B–C Ring System of Lysergic Acid via Vilsmeier–Haack‐Type Cyclization of 1H‐Indole‐4‐propanoic Acid Derivatives

Vilsmeier–Haack‐type cyclization of 1H‐indole‐4‐propanoic acid derivatives was examined as model construction for the A–B–C ring system of lysergic acid ( 1 ). Smooth cyclization from the 4 position of 1H‐indole to the 3 position was achieved by Vilsmeier–Haack reaction in the presence of K₂CO₃ in MeCN, and the best substrate was found to be the N,N‐dimethylcarboxamide 9 (Table 1). The modified method can be successfully applied to an α‐amino acid derivative protected with an N‐acetyl function, i.e., to 27 (Table 2); however, loss of optical purity was observed in the cyclization when a chiral substrate (S)‐ 27 was used (Scheme 5). On the other hand, the intramolecular Pummerer reaction of the corresponding sulfoxide 20 afforded an S‐containing tricyclic system 22 , which was formed by a cyclization to the 5 position (Scheme 3).     

A Practical and Enantiospecific Synthesis of (−)‐(R)‐ and (+)‐(S)‐Piperidin‐3‐ols

A highly enantiospecific, azide‐free synthesis of (?)‐(R)‐ and (+)‐(S)‐piperidin‐3‐ol in excellent yield was developed. The key step of the synthesis involves the enantiospecific ring openings of enantiomerically pure (R)‐ and (S)‐2‐(oxiran‐2‐ylmethyl)‐1H‐isoindole‐1,3(2H)‐diones with the diethyl malonate anion and subsequent decarboxylation.     

Diastereoselective Electrophilic Amination of Chiral 1‐Benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1H)‐one for the Asymmetric Syntheses of α‐Substituted α,β‐Diaminopropanoic Acids

The chiral compounds (R)‐ and (S)‐1‐benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1H)‐one ((R)‐ and (S)‐ 1 ), derived from (R)‐ and (S)‐asparagine, respectively, were used as convenient starting materials for the preparation of the enantiomerically pure α‐alkylated (alkyl=Me, Et, Bn) α,β‐diamino acids (R)‐ and (S)‐ 11 – 13 . The chiral lithium enolates of (R)‐ and (S)‐ 1 were first alkylated, and the resulting diasteroisomeric products 5 – 7 were aminated with ‘di(tert‐butyl) azodicarboxylate’ (DBAD), giving rise to the diastereoisomerically pure (≥98%) compounds 8 – 10 . The target compounds (R)‐ and (S)‐ 11 – 13 could then be obtained in good yields and high purities by a hydrolysis/hydrogenolysis/hydrolysis sequence.     

Reaction of Optically Active Oxiranes with Thiofenchone and 1‐Methylpyrrolidine‐2‐thione: Formation of 1,3‐Oxathiolanes and Thiiranes

The SnCl₄‐catalyzed reaction of (?)‐thiofenchone (=1,3,3‐trimethylbicyclo[2.2.1]heptane‐2‐thione; 10 ) with (R)‐2‐phenyloxirane ((R)‐ 11 ) in anhydrous CH₂Cl₂ at ?60° led to two spirocyclic, stereoisomeric 4‐phenyl‐1,3‐oxathiolanes 12 and 13 via a regioselective ring enlargement, in accordance with previously reported reactions of oxiranes with thioketones (Scheme 3). The structure and configuration of the major isomer 12 were determined by X‐ray crystallography. On the other hand, the reaction of 1‐methylpyrrolidine‐2‐thione ( 14a ) with (R)‐ 11 yielded stereoselectively (S)‐2‐phenylthiirane ((S)‐ 15 ) in 56% yield and 87–93% ee, together with 1‐methylpyrrolidin‐2‐one ( 14b ). This transformation occurs via an S_N2‐type attack of the S‐atom at C(2) of the aryl‐substituted oxirane and, therefore, with inversion of the configuration (Scheme 4). The analogous reaction of 14a with (R)‐2‐{[(triphenylmethyl)oxy]methyl}oxirane ((R)‐ 16b ) led to the corresponding (R)‐configured thiirane (R)‐ 17b (Scheme 5); its structure and configuration were also determined by X‐ray crystallography. A mechanism via initial ring opening by attack at C(3) of the alkyl‐substituted oxirane, with retention of the configuration, and subsequent decomposition of the formed 1,3‐oxathiolane with inversion of the configuration is proposed (Scheme 5).