不对称催化氢化制备（S）—（＋）—萘普生：Ⅰ.不对称催化剂的合成及催化性能

全过程合成出手性双膦配体２，２’－双（二苯基膦）－６，６’－二甲基联苯，以金属钌为中心原子，制备出几种不对称催化剂。通过考察不对称氢化制备（Ｓ）－（＋）－萘普生的反应光学收率，研究了催化剂的催化性能，并与联萘型双膦配体催化剂进行了比较。     

有机溶剂—水以液相体系脂肪酶不对称水解合成S—（＋）—萘普生

采用有机溶剂－水双液相体系作为反应介质，并用键合有一Ｃ６Ｈ５的无定型多孔硅胶作为分散在两相间的接触面。用圆柱状假丝酵母脂肪酶对萘普生甲酯进行不对称水解，考察了酶浓度、体系ＰＨ值、温度、分散剂对反应的影响，当转化率为２４．３％时，产品萘普生的对映体守量值为９４．９％，剩余底物萘普生甲酯的对映体过量值为３０．５％，当以异辛烷作为有机相时，该体系酶催化水解的对映体比率约为５０。     

钯催化α-(6-甲氧基-2-萘基)乙醇的不对称羰基化反应

不对称羰基化可产生多种手性分子，而这些手性分子是合成药物和农药等重要前体［１］．光学活性的α－芳基丙酸类如Ｓ－布洛芬和萘普生是很重要的非麻醉性镇痛消炎药．以不对称氢甲酰化反应和氢羧基化反应制备光学活性的布洛芬和萘普生已有报道［２，３］，但这些不对称羰...     

有机溶剂-水双液相体系脂肪酶不对称水解合成S-(+)-萘普生

采用有机溶剂－水双液相体系作为反应介质，并用键合有—Ｃ６Ｈ５的无定型多孔硅胶作为分散剂增大两相间的接触面，用圆柱状假丝酵母脂肪酶对萘普生甲酯进行不对称水解．考察了酶浓度、体系ｐＨ值、温度、分散剂对反应的影响．当转化率为２４．３％时，产品萘普生的对映体过量值（ｅｅ）为９４．９％，剩余底物萘普生甲酯的对映体过量值（ｅｅ）为３０．５％，当以异辛烷作为有机相时，该体系酶催化水解的对映体比率（Ｅ）约为５０．     

膜反应器中萘普生甲酯的动态拆分

在碱催化连续原位消旋条件下,利用CRL脂肪酶（Candida rugosa lipase）催化的萘普生甲酯立体选择性水解反应。动态拆分制备（S）－普生。使用硫水硅橡胶膜隔离生物催化拆分反应和碱催化消旋反应,解决了常规动态拆分反应中生物催化剂难以承受原位化学消旋苛刻反应条件的难题。为了利于从水－有机溶剂乳化体系中分离产物和克服产物抑制,将亲水半透膜引入搅拌罐反应器,在该膜反应器中进行动态拆分反应。当转化率超过60％时,产物（S）－萘普生的对映体过量值（eep)仍在96％以上,在反应过程中还发现CRL脂肪酶同工酶的转化。     

PVP—PdCI2—CuCI2／PPh3体系催化α—（6‘甲氧基—2’—萘基）乙醇羰化反应研究

首次用高分子负载型双金属催化剂PVP－PdCI2-CuCI2/PPh3体系催化α-（6'甲氧基－2'－萘基）乙醇与一氧化碳及甲醇进行碳化反应制备萘普生甲酯,分别对温度、压力、时间、P／Pd比等影响因素进行了考察,在反应条件为100℃、16-20h、CO压力为4．0MPa、P/Pd＝3时,转化率可达97．4％,异正比为14．4,在同样条件下制备萘普生乙酯及萘普生异丙酯,转化率及选择性均有明显下降。另外,该催化剂体系也可催化其它类型α－芳基乙醇的羰化反应。     

手性高效液相色谱法测定1—（6‘—甲氧基萘）乙醇不对称氢酯基化反应

在自制的硅基纤维素－三（３，５－二甲基苯基氨基甲酸酯）高效液相色谱手性固定相上（ＨＰＬＣ－ＣＳＰ），优化了１－（６＇－甲氧基萘）乙醇氢酯基化反应产物－萘普生甲酯手性分离的条件，测定了相应的一系列不对称氢酯基化反应产物的对映体过剩值（ｅ．ｅ．值）。结果表明，在ＣＤＭＰＣ－ＣＳＰ手性柱上用ＨＰＬＣ测定此类不对称催化反应的光学产率，评价催化剂体系的手性选择是一种非常理想的方法。     

对萘普生和萘普生甲酯的毛细管电泳手性分离

以磺化β－ＣＤ作为手性分离添加剂,分别对萘普生和萘普生甲酯进行了手性分离研究,当磺化β－ＣＤ的浓度为３．５％（Ｗ／Ｖ）时,萘普生和萘普生甲酯的手性分离度都可大于２,但萘普生与萘普生甲酯不能达到同时拆分。如果同时以磺化β－ＣＤ和ＨＰ－β－ＣＤ作为作为手性分离添加剂,则可对萘普生甲酯达到同时拆分,当磺化β－ＣＤ和ＨＰ－β－ＣＤ的浓度分别为３．５％和１．５％（Ｗ／Ｖ）时,对萘磺生和萘普生甲酯两种消旋体的     

反相键合相高效液相色谱法分离测定萘普生

 建立了分离测定萘普生和溴代萘普生的反相键合相高效液相色谱法。采用ＯＤＳ柱，以添加５０ｍｍｏｌ／Ｌ乳酸并用高氯酸调节ｐＨ为２．５的８０％甲醇－水溶液作为流动相，以苯甲酸为内标物，测定了不对称合成工艺产物中萘普生和溴代萘普生的含量。方法的准确度分别为９９．８３％～１０２．０７％（萘普生）和９９．０％～１００．８３％（溴代萘普生），相对标准偏差分别小于２．５８％（萘普生）和３．６４％（溴代萘普生）。方法可用于工艺条件的选择和质量检测。     

反相键合相高效液相色谱法分离测定萘普生

建立了分离测定萘普生和溴代萘普生的反相键合相高效液相色谱法。采用ＯＤＳ柱，以添加５０ｍｍｏｌ／Ｌ乳酸并用高氯酸调节ｐＨ为２．５的８０％甲醇－水溶液作为流动相，以苯甲酸为内标物，测定了不对称合成工艺产物中萘普生和溴代萘普生的含量。方法的准确度分别为９９．８３％～１０２．０７％（萘普生）和９９．０％～１００．８３％（溴代萘普生），相对标准偏差分别小于２．５８％（萘普生）和３．６４％（溴代萘普生）。方法可用于工艺条件的选择和质量检测。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Catalyst free,visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes

An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C₆₀ and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C₆₀, followed by SET from the amine to the triplet excited state of C₆₀. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding α-amino radical which couples with the C₆₀ radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared.     

Highly efficient and stereoselective cycloaddition of nitrones to indolyl- and pyrrolylacrylates

The reactions of various nitrones with indolyl- and pyrrolylacrylates proceeds regioselectively with high diastereoselectivity in the case of aldonitrones, and represents an effective method for obtaining new indolyl- and pyrrolyl-substituted isoxazolidine carboxylates stabilized by weak (CH?O) and moderate (NH?N) strength intramolecular hydrogen bonding. The resulting cycloadducts exhibit promising in vitro anti-influenza activities.     

Transition metal-free direct amination of benzoxazoles using formamides as nitrogen sources

A transition metal-free method for the direct amination of benzoxazoles using formamides as nitrogen sources is reported, which was mediated by an inexpensive and environmentally friendly tetrabutylammonium iodide/tert-butyl hydroperoxide system and gave the 2-aminobenzoxazole derivatives with moderate to good yields.     

l-Proline-catalyzed five-component domino reaction leading to multifunctionalized 1,2,3,4-tetrahydropyridines

Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl₃-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction.     

Exploring the scope of the Gewald reaction: Expansion to a four-component process

An efficient four-component reaction was developed to take advantage of the reactivity of the 2-aminothiophene-3-carbonitrile functionality, which is obtained during the classical three-component Gewald reaction. Various α-methylene bearing ketones were reacted with malononitrile, elemental sulfur, and aryl/heteroarylnitrile derivatives in t-BuOH/NaOH to afford 2-arylthieno[2,3-d]pyrimidin-4-amines in high yields. Preliminary studies revealed the photophysical properties of the products and their potential for use as metal sensors.