顺式-二(乙二胺)二硝基合钴(Ⅲ)苹果酸盐的晶体结构及手性识别

合成了标题化合物，并用X-射线衍射法确定了该分子的晶体结构。化合物Δ（λλ），Λ（δδ）－cis－[Co（en）2（NO2）2]2d，l-C4H4O5，Co2C12N12O13H22，Mr=657．94．晶体属单斜晶系，空间群为P21/c，晶胞参数：a=13．969（4），b=6.440（1），c＝14．408（4）A，β=94.37（1）°，V=1292．3A3，Z=2，Dc=1．69g／cm3，μ=105.833cm－1，F（000）=668.最终偏离因子R=0.066，Rw=0．085。结构分析表明晶体存在无序现象，其阴离子C4H4O52-有两种排列方式。R-构型和S-构型的几率各为50％，手性识别是通过Δ构型的阳离子与阴离子R-构型C原子上羟基氧形成氢键相互作用；Λ构型的阳离子与阴离子S-构型C原子上羟基氧形成氢键相互作用而实现的。     

一锅法合成3-溴丙基乙酸酯

以1，3-丙二醇、氢溴酸（48％）和冰醋酸为原料，在带水剂的作用下，一锅法合成了3-溴丙基乙酸酯．考察了带水剂及追加醋酸或醋酸酐量对产率的影响，并通过气质联用仪对粗产品进行分析测定，推断其反应机理．结果表明：较适宜的合成条件为1，3-丙二醇0．21mol，1，3-丙二醇与氢溴酸（48％）、冰醋酸摩尔比为1：1：1．3，在带水剂甲苯（21mL）的作用下，反应2．5h，反应结束前1h追加4．8mL醋酸酐，合成效果最好，产率可达到95．7％．     

4-羟基联苯4’-甲酸-L-2-甲基丁醇酯的合成

以4-羟基联苯，4-羟基4’-氰基联苯和手性L-2-甲基丁醇为原料，通过三条路线合成了铁电性液晶中间体4-羟基联苯4’-甲酸-L-2-甲基丁醇酯。5步法（醚化、酰化、溴仿、水解和酯化）总收率35．6％；3步法（酰化、溴仿和酯化）总收率50．7％；而以4-羟基-4＇-氰基联苯为原料的一步合成法收率64．4％。中间体和目标产物的结构经^1H NNR和IR确证。     

新方法合成（Z）-5-氟-2-甲基-1-[（4-甲基亚磺酰苯基）亚甲基]-1H-茚-3-乙酸及其X-单晶衍射分析

以对甲亚磺酰基苄溴为原料，通过4步反应合成得到立体专一性的Z式构型产物（Z）-5-氟-2-甲基-1-[（4-甲基亚磺酰苯基）亚甲基]-1H-茚-3-乙酸（Sulindac舒林酸）。X-单晶衍射分析舒林酸分子中共存有强和弱的分子间氢键。     

法呢基苯乙酮及其黄烷酮化合物的全合成

以2，4，6-三羟基苯乙酮和法呢基溴为原料，经一步反应以52．0％和6．5％的收率同时得到3-法呢基-2，4，6-三羟基苯乙酮（1）和4-法呢氧基-2，6-二羟基苯乙酮（2）；然后以化合物1和3，4-二羟基苯甲醛为原料，经羟基保护、缩合、环化和去保护基共6步反应，以19．8％的总收率全合成了（±）-6-法呢基-3'，4'，5，7-四羟基黄烷酮（3）．化合物1、2和3均是从澳大利亚植物Borroniaramosa中分离得到的新天然产物，此次为首次合成．     

氯化亚锡催化合成环缩醛

通过正交实验确定了氯化亚锡催化合成正丁醛缩1,2-丙二醇的最佳工艺条件为：正丁醛200mmol,n（正丁醛）：n（1,2-丙二醇）=1．0：1．5,氯化亚锡3g,环己烷13mL,回流分水1h,收率76．35％。并在此条件下合成了多种环缩醛,收率62．18％～81．90％。催化剂可重复使用。     

2-（4-溴苯甲基）-苯并咪唑的合成及缓蚀性能

以对溴苯乙腈和邻苯二胺为原料，在磷酸和多聚磷酸混合酸的催化下，合成了2-（4-溴苯甲基）-苯并咪唑（BBBI）．利用红外、碳谱、氢谱、元素分析等方法对产物进行了结构表征．采用电化学极化曲线法考察了BBBI在5％硫酸溶液中对铜的缓蚀作用，通过对比实验表明BBBI对铜电极腐蚀有较好的缓蚀效果．     

N-苯基-3-(p-氯苯)全氢螺[苯并[b]异■唑7,1′环己烷]-4酮的合成及晶体结构

合成并测定了N-苯基-3－（p-氯苯）全氢螺[苯并[b]异唑7，1-环已烷]-4-酮（3）的单晶结构，晶体分子式C24H26ClNO2,Mr=395.93，晶体属单科晶系，空间群为P21／c，晶胞参数结构的偏离因子R=0．037，Rw=0．039。分子3存在着两个螺六员环（A和B），A环具有通常的椅式构型，B环是扭船式构型。B环和五员异呼吐环C环并连，C环有些扭曲，结构分析结果表明，分子3具有“顺-顺”构型。     

手性八配位镧系络合物的立体化学与固体CD光谱

本文立体选择性地合成了八配位Ln（III）络合物[Eu（dbm）3L^RR]（1）、[Eu（dbm）3L^SS]（2）和[Tb（dbm）3L^RR]（3）（L^RR／L^SS=（-）／（＋）-4,5-蒎烯基联吡啶,Hdbm=二苯甲酰甲烷）,利用单晶衍射、Uv-vis和固体CD光谱对其进行了表征．晶体结构分析和固体CD光谱表明1和2互为对映体．采用激子手性方法,通过与六配位和七配位的β-二酮络合物的固体CD光谱的对比,提出含β-二酮的八配位Ln（III）络合物的绝对构型关联规则．该系列络合物的畸变四方反棱柱的△或∧绝对构型也被其单晶结构所证实．     

钨硅酸的制备及其在催化合成缩酮(醛)中的应用

本文探讨了钨硅酸的制备方法,以合成环己酮1,2-内二醇缩酮为例验证钨硅酸的催化活性,并探讨了合成其它缩酮（醛）的适宜条件,得到的收率分别为：环己酮1,2-丙二醇缩酮85．5％、环己酮乙二醇缩酮89．6％、丁酮乙二醇缩酮79．5％、丁醛乙二醇缩醛89．1％、丁醛1,2丙二醇缩醛81．5％。     

Design of Selenium‐Based Chiral Chemical Probes for Simultaneous Enantio‐ and Chemosensing of Chiral Carboxylic Acids with Remote Stereogenic Centers by NMR Spectroscopy

Selenium‐based enantiopure chiral chemical probes have been designed in a modular way starting from available amino alcohols. The probes developed were found to be efficient in chemoselective interaction with carboxylic functions of chiral substrates leading to diastereomeric amide formation and in sensing α‐, β‐, and remote (up to seven bonds away from the carboxylic group) chiral centers by using ⁷⁷Se NMR spectroscopy. As a result, it was possible to determine the enantiomeric ratio of structurally diverse individual chiral acids including polyfunctional compounds and drugs with high accuracy. An approach to analyzing the crude reaction mixtures has been successfully developed by using bifunctional selenium‐ and fluorine‐containing chiral probes. More importantly, it was revealed that, based on the ⁷⁷Se NMR data obtained, it is possible to obtain primary information about the location and nature of the substituents at the chiral center (chemo‐ and enantiosensing), which can simplify the structural elucidation of complex compounds. The derivatization procedure takes as little as 5 min and can be performed directly in an NMR tube followed by NMR measurements without any isolation and purification steps.     

新型多氢键双功能手性酰胺类化合物的高效合成

以BINOL-3,3′-二羧酸为原料,经外消旋化合物的拆分和缩合反应,合成了7个新型的联二萘骨架手性酰胺类化合物,收率51%~70%,其结构经¹H NMR, ¹³C NMR, FT-IR, HR-MS（ESI）和元素分析表征。     

Synthesis of novel chiral compounds of purine and pyrimidine bases

The physiologically active groups such as purine and pyrimidine bases are introduced to the asymmetric ynthesis. The optically pure compounds bearing purine and pyrimidine bases (5a—5e) were prepared via the asymetric Michael addition reaction of purines and pyrimidines as Michael donators with the chiral source 5-(R)-[(1R, 2S, 5R)-menthyloxy]-2(5H)-furanone (3a), which was prepared from the natural chiral auxiliary (-)-menthol. The synthetic method was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]_D~(20), IR, UV, ~1H NMR, ~(13)C NMR and MS. The absolute configuration of 5a was established by X-ray crystallography. The results provided an efficient synthetic route to chiral purines and pyrimidine analogues, and offered chiral sources for further research on the physiologically active compounds of chiral nucleotides.     

16种手性化合物在不同自制手性固定相上的拆分比较

采用高效液相色谱法,在自制的纤维素-三(3,5-二甲基苯基氨基甲酸酯)(ATEO-OD)、纤维素-三(4-甲基苯基氨基甲酸酯)(ATEO-OG)和纤维素-三(4-甲基苯基甲酸酯)(ATEO-OJ)3种手性柱上对16种不同结构的手性化合物进行了拆分和比较.试验结果表明:16个手性样品在这3种手性固定相上分别获得了不同程度的拆分,A TEO-OD对所分析样品具有更好的手性识别能力,ATEO-OG和ATEO-OJ的手性识别能力相当.     

A New Approach to the Asymmetric Reaction of the Chiron 5－L－Menthyloxy－2（5H）－furanones with Horner－Emmons Reagent

The asymmetric reaction of the chiron 2(5H )-furanones (4a-4c) with the Horner-Emmons reagents (5a-5b) has been investigated. The newly chirai organophosphorus derivatives 6 and 7 were obtained using the phosphoryl-stabilized carbanion as a building block in DMSO under mild conditions. Through the asymmetric introduction, the Horner-Emmons reagent could be transformed to a chiral building block to afford the novel functionalized phosphorus derivatives. The structures of the synthesized compounds 6 and 7 were identified on the basis of their elementary and spectroscopic data, such as IR,^1H NMR, ^13C NMR, MS and X-ray crystallography. These resuits provided a valuable approach to the synthesis of potentially interesting chirai organophosphorus derivatives and probing their biological activities.     

Quantitative 1H NMR method for the routine spectroscopic determination of enantiomeric purity of active pharmaceutical ingredients fenfluramine, sertraline, and paroxetine

Determining the enantiomeric purity of chiral therapeutic agents is important in the development of active pharmaceutical ingredients (API). A strategy for determining the enantiomeric purity of three APIs was developed using nuclear magnetic resonance (NMR) and the chiral solvating agent (CSA) 1,1-bi-2-naphthyl (1). While chiral chromatography is widely used to evaluate enantiomeric purity, it can sometimes suffer from tedious sample preparation obviating rapid measurements that are sometimes needed during the manufacture of such agents. The techniques described herein provide comparable enantiomeric purity results with those obtained with traditional chiral HPLC and other published methods for these compounds. Chiral analysis of standard samples of methylbenzylamine enantiomeric mixtures using 1 were found to be quantitative to approximately 1% minor enantiomer. Enantiomeric purity determination by NMR utilizing chiral solvating agents do not require special instrumental techniques, chemical derivatization or standards and is therefore ideally suited for rapid routine analysis. As a result, the technique demonstrated is commonly used in our laboratory as a complementary or alternative method to chiral HPLC or optical rotation measurements for routine determination of enantiomeric purity.     

Straightforward solvent-free synthesis of new chiral benzene-1,3,5-tricarboxamides

A new series of chiral benzene-1,3,5-tricarboxamides (BTAs) 3a–e was prepared using the ecofriendly solvent-free approach, starting with benzene-1,3,5-tricarbonyl chloride 1 and appropriate optically pure primary amines 2a–e. All the reactions occur in a short time with excellent yields (>90%). The structures of the compounds have been characterized by Fourier transform infrared spectroscopy (FT–IR), Proton nuclear magnetic resonance (1H NMR), Carbon 13 nuclear magnetic resonance (13C NMR), electron ionization mass spectrometry (EI–MS), and elemental analysis.     

D-甘露醇衍生的新型手性硫脲的合成及其在Henry反应中的应用

以D-甘露醇为原料,经缩合,醇解,叠氮化和还原等4步反应制得含联1,3-二氧六环骨架的手性胺中间体(4); 4分别与3,5-双(三氟甲基)苯基异硫氰酯,表奎宁异硫氰酸酯和表奎尼丁异硫氰酸酯偶联合成了3个新型的手性硫脲(6a~6c),其结构经¹H NMR, ¹³C NMR, IR和HR-MS表征。以硝基甲烷和苯甲醛的不对称Henry反应为探针反应,考察了6的催化活性。结果表明：在以吡啶为碱,甲苯为溶剂,6b 5%(摩尔百分数),于-30 ℃反应24 h的条件下,(S)-2-硝基-1-苯基乙醇的收率和对映选择性分别为69%和78%。     

Synthesis and Antiviral Activities of Chiral Thiourea Derivatives

An environmentally benign method has been developed for the synthesis of novel chiral thiourea derivatives in high yields in ionic liquid [Bmim]PF6. The ionic solvent can be recovered and reused without any loss of its activity. The target compounds were characterized by elemental analysis, IR, 1H NMR and 13C NMR spectral data. According to the preliminary bioassay, some of the chiral thiourea analogues exhibited moderate in vivo antiviral activities against TMV at a concentration of 500 mg/L. Title chiral compound 3i was found to possess good in vivo protection, inactivation and curative activities of 57.0%, 96.4% and 55.0%, respectively against TMV with an inhibitory concentration at 500 mg/L. The title chiral compound 3i revealed better inactivation effect on TMV (EC50＝50.8 µg/mL) than Ningnanmycin (EC50＝60.2 µg/mL).     

手性膦酸二酯类化合物的合成与结构

手性呋喃酮1a1b与亚磷酸三酯2a2b通过串联的不对称Michael加成/分子内Michalis-Arbazov重排反应,得到含磷官能团的新手性化合物5-(S)-(1S)-冰片氧基-4-膦酸二酯基-3-卤素-2(5H)-呋喃酮(3a～3d).该反应具有条件温和,产率高(69%～93%),光学纯度单一(d.e.≥98%)等特点.通过元素分析,IR,UV¹HNMR¹³CNMR,MS,[α]_D²⁰等分析数据以及X射线四圆衍射确定了它们的化学结构和绝对构型.