鱼藤酮类衍生物的研究进展

鱼藤酮类衍生物是一类从鱼藤属等植物中提取出来的具有杀虫活性的异黄酮类化合物. 从1932年至今, 已经从植物中提取分离出47种鱼藤酮类化合物. 这一类化合物之所以具有很好的杀虫活性, 是由于对还原型烟酰胺腺嘌呤二核甘酸(NADH)的抑制作用而阻断了线粒体的呼吸. 对天然鱼藤酮类衍生物的结构、活性和合成方面的研究分别进行了概括.     

Synthesis of Pseudobaptigenin Analogs

Homologs of the natural isoflavonoid pseudobaptigenin containing benzodioxane and benzodioxepane fragments were synthesized. Methanesulfonyl, carbamoyl, aminomethyl, and coumarin-containing isoflavone derivatives were prepared.     

Synthesis of aminomethyl derivatives of sophoricoside

Aminomethylation of the natural isoflavonoid sophoricoside (genistein-4-O-β-D-glucoside) was studied. It was shown that the most convenient method for performing the aminomethylation was the use of aminals. 6,8-bis-Substituted derivatives of sophoricoside were synthesized.     

Total Synthesis and Activity of the Metallo‐β‐lactamase Inhibitor Aspergillomarasmine A

Resistance to β‐lactam antibiotics is mediated primarily by enzymes that hydrolytically inactivate the drugs by one of two mechanisms: serine nucleophilic attack or metal‐dependent activation of a water molecule. Serine β‐lactamases are countered in the clinic by several codrugs that inhibit these enzymes, thereby rescuing antibiotic action. There are no equivalent inhibitors of metallo‐β‐lactamases in clinical use, but the fungal secondary metabolite aspergillomarasmine A has recently been identified as a potential candidate for such a codrug. Herein we report the synthesis of aspergillomarasmine A. The synthesis enabled confirmation of the stereochemical configuration of the compound and offers a route for the synthesis of derivatives in the future.     

Reactions of furocoumarins. II. Synthetic aminomethyl psoralens via chloromethylation or benzylic bromination

Several psoralen derivatives have been synthesized in order to evaluate their efficacy as photochemotherapeutic (PUVA) agents, including a variety of 4′-substituted-4,5′,8-trimethypsoralen compounds ( 1d-j ). Improved synthesis of the very potent photosensitizers 8-methylpsoralen ( 6a ) and 4,8-dimethylpsoralen ( 6b ) are described and 6a has been shown to undergo formylation in the 4′-position. Free radical bromination of 6a and 6b with NBS affords primarily 8-bromomethyl derivatives ( 8a and d ), which are readily converted into the 8-aminomethyl derivatives ( 8c and f ) by the Gabriel method. If the 4′-position is blocked, electrophilic substitution apparently occurs primarily in the 5′-position of the psoralen system. At least, chloromethylation of 4′-methylpsoralen ( 9 ) affords mainly 5′-chloromethyl derivatives ( 10a and d ), which also lead to aminomethylpsoralens ( 10c and f ).     

Changes in the anti-inflammatory activity of soy isoflavonoidgenistein versus genistein incorporated in two types of cyclodextrin derivatives

ABSTRACT: BACKGROUND: The isoflavonoid genistein represents the major active compound from soybean, the vegetalproduct from Glycine max (Fabaceae). The aim of this study is to prove that genistein wasincorporated in two semisynthetic cyclodextrins, beta-cyclodextrin derivatives:hydroxypropyl-beta-cyclodextrin and randomly-methylated-beta-cyclodextrin as well as to compare the anti-inflammatory activity of genistein with that of genistein incorporated inthese two types of semisynthetic cyclodextrins. RESULTS: The animal studies were conducted on 8-week old C57BL/6 J female mice. Inflammation wasinduced in both ears of each mouse by topical application of 10 micrograms 12-Otetradecanoylphorbol-3-acetate dissolved in 0.1 ml solvent (acetone : dimethylsulfoxide in amolar ratio 9:1). Thirty minutes later treatment was applied. The inflammatory reaction wascorrelated with increased values in ear thickness. Treatment with genistein and genisteinincorporated in the two cyclodextrins led to decreased values for ear thickness. Better antiinflammatoryaction was found for the complexes of genistein. Both haematoxylin-eosinanalysis and CD45 marker expression are in agreement with these findings. CONCLUSIONS: Results allow concluding that genistein is an active anti-inflammatory phytocompound andits complexation with hydrophilic beta-cyclodextrin derivatives leads to a stronger antiinflammatoryactivity.     

Phthalones and their structural analogs (review)

This review is devoted to research on the synthesis, reactivities, practical application, and structural problems of compounds of the phthalone series, primarily pyrophthalones and quinophthalones. The properties and peculiarities of the structures of the indicated compounds are compared with structural analogs that contain other heterocyclic substituents and other β-dicarbonyl systems and also with other betainelike derivatives of β-dicarbonyl compounds. Problems in the development of the chemistry of phthalones are discussed.     

The first example of a diastereoselective thio-Ugi reaction: a new synthetic approach to chiral imidazole derivatives

The first example of a diastereoselective thio-Ugi reaction with chiral alpha-methylbenzylamine is described. The reaction results in formation of two diastereomers of thioamides, the major of which was isolated. We have found that under similar conditions stereochemical results of the thio-Ugi reaction are opposite to stereochemical results of the Ugi reaction. Several chiral thioamides were synthesized. The reaction of thioamides with ammonia results in substituted amidines, which can be cyclized to imidazole derivatives in aqueous HCl. The synthesis of chiral imidazole derivatives was elaborated. Using certain approaches, both isomers of a key synthon in the synthesis of SB203386 (an orally bioactive HIV-1 protease inhibitor) were prepared. The scope, limitations, and stereochemistry of the approach are discussed.     

Azaacene Dimers: Acceptor Materials with a Twist

The synthesis of five spiro-linked azaacene dimers is reported and their properties are compared to that of their monomers. Dimerization quenches emission of the longer (≥(hetero)tetracenes) derivatives and furnishes amorphous thin-films, the absorption is not affected. The larger derivatives were tested as acceptors in bulk-heterojunction photovoltaic devices with a maximum power conversion efficiency of up to 1.6 %.     

Biological potential of pyrimidine derivatives in a new era

Pyrimidine and its derivatives play a wide role in drug discovery processes and have considerable chemical significance and biological activities. Pyrimidines are the building blocks of many natural compounds such as vitamins, liposacharides, and antibiotics. Pyrimidine is used as parent substance for the synthesis of a wide variety of heterocyclic compounds and raw material for drug synthesis and is also crucial in the theoretical development of heterocyclic chemistry and in organic synthesis. Pyrimidine derivatives are vital in several biological activities, i.e. antihypertensive, anticancer, antimicrobial, anti-inflammatory, and antioxidant activity. This creates interest among researchers who have synthesized a variety of pyrimidine derivatives.     

Identification of isoflavonoids in several kudzu samples by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry

Pueraria lobata is a rich source of isoflavonoids. The detection and identification of isoflavonoid components from Pueraria radix (RP), callus and cell cultures, is very important for the safest and most effective use of kudzu as a medicinal plant, and for the studies on quantitative analysis and secondary metabolism of isoflavonoids in vitro cultures. Liquid chromatography is coupled with negative and positive electrospray ionization (ESI) tandem mass spectrometry (MS-MS), and photodiode array detection is used to characterize and detect isoflavonoids in root, callus, and cell samples of P. lobata. Characteristic product ions of aglycones, O-glucosides, and C-glucosides were obtained from the full-scan ESI-MS chromatography of the major peaks and the MS-MS spectra of the protonated ions. Five major components of puerarin, daidzin-6"-O-acetylester, genistin-6"-O-malonylester, biochanin A-7-O-glucoside-6"-O-malonylester, and daidzein are detected and identified from the methanolic extract of P. lobata callus cultures. The major isoflavonoid components of P. lobata cell suspension cultures are identified as puerarin, daidzin, daidzin-6"-O-acetylester, genistin-6"-O-malonylester, biochanin A-7-O-glucoside-6"-O-malonylester, genistein-8-C-glucoside-6"-O-malonylester, and daidzein, on the basis of ESI-MS and MS-MS spectra analysis. Likewise, puerarin, daidzin, genistein-6"-O-malonylester, 3'-methoxypuerarin, and daidzein are detected and identified from RP. Of those isoflavonoid components detected, daidzin-6"-O-acetylester is a new isoflavonoid glucoside and is for the first time detected from P. lobata cultures in vitro.     

Scope of a novel three-component synthesis of highly functionalized pyridines(dagger)

A mechanistically unique three-component synthesis provides a variety of functionalized pyridine derivatives in fair to excellent yields. The scope of this reaction was studied with respect to the alkoxyallene, the nitrile, and the carboxylic acid. Due to the 4-hydroxy group, these pyridine derivatives are suitable precursors for subsequent palladium-catalyzed reactions. Suzuki couplings of the corresponding pyridyl nonaflates lead to a variety of pyridine and bipyridine derivatives.     

Toward a Greener World—Cyclodextrin Derivatization by Mechanochemistry

Cyclodextrin (CD) derivatives are a challenge, mainly due to solubility problems. In many cases, the synthesis of CD derivatives requires high-boiling solvents, whereas the product isolation from the aqueous methods often requires energy-intensive processes. Complex formation faces similar challenges in that it involves interacting materials with conflicting properties. However, many authors also refer to the formation of non-covalent bonds, such as the formation of inclusion complexes or metal–organic networks, as reactions or synthesis, which makes it difficult to classify the technical papers. In many cases, the solubility of both the starting material and the product in the same solvent differs significantly. The sweetest point of mechanochemistry is the reduced demand or complete elimination of solvents from the synthesis. The lack of solvents can make syntheses more economical and greener. The limited molecular movements in solid-state allow the preparation of CD derivatives, which are difficult to produce under solvent reaction conditions. A mechanochemical reaction generally has a higher reagent utilization rate. When the reaction yields a good guest co-product, solvent-free conditions can be slower than in solution conditions. Regioselective syntheses of per-6-amino and alkylthio-CD derivatives or insoluble cyclodextrin polymers and nanosponges are good examples of what a greener technology can offer through solvent-free reaction conditions. In the case of thiolated CD derivatives, the absence of solvents results in significant suppression of the thiol group oxidation, too. The insoluble polymer synthesis is also more efficient when using the same molar ratio of the reagents as the solution reaction. Solid reactants not only reduce the chance of hydrolysis of multifunctional reactants or side reactions, but the spatial proximity of macrocycles also reduces the length of the spacing formed by the crosslinker. The structure of insoluble polymers of the mechanochemical reactions generally is more compact, with fewer and shorter hydrophilic arms than the products of the solution reactions.     

CZE Determination of Calixarenes and Related Derivatives Using Acetonitrile as a Modifier

The applications of third-generation host compound calixarenes have been restricted due to their high price and shortage of supply. To obtain high pure calixarenes with high yield, synthesis strategy and analytical method investigations are necessary. The present work describes capillary zone electrophoresis (CZE) for the separation and determination of calixarene derivatives under the optimized CZE conditions within 20 min. The CZE method was evaluated with linear ranges, detection limits, recoveries and repeatability. The results indicated that the method was accurate and reproducible. As expected, it could be utilized to separate and evaluate calixarene derivatives during their synthesis and purification.     

The phenolic oxidation of a β-methylchalcone

The phenolic oxidation of 2',4-dihydroxy-4'-methoxy-β-methylchalcone using alkaline potassium ferricyanide gives an aurone rather than an isoflavone. This result is discussed in the context of current theories regarding the biosynthesis of flavonoid and isoflavonoid compounds.     

New Type of an Adsorption Layer of Organic Molecules with a Cage Structure Condensed at the Electrode/Solution Interface: The Adsorption of Cubane Derivatives on a Mercury Electrode

A synthesis and a study by method of measuring the differential capacitance on a stationary mercury drop of the adsorption of a number of cubane derivatives in a surface-inactive electrolyte are performed. It is established that the compounds studied exhibit a high surface activity. For bromine derivatives of cubane (4-bromomethoxycarbonylcubane, 4-bromohydroxymethylcubane) the formation of two-dimensional adsorption layers is discovered. Values of adsorption parameters for these compounds are evaluated with use made of the Frumkin isotherm.     

固定化脯氨酸及其衍生物用于催化不对称有机合成

脯氨酸及其衍生物作为有机手性催化剂,在不对称有机合成中得到广泛应用。该类催化剂具有结构简单、来源丰富和选择性高等优点,但仍存在催化剂用量大、难以回收以及无法重复利用等不足。近年来,随着固定化技术的发展,固定化脯氨酸及其衍生物受到广泛关注。固定化脯氨酸及其衍生物催化剂可以简化不对称催化中产物的分离过程,实现催化剂的便利回收与循环使用。本文综述了固定化脯氨酸及其衍生物的制备及在催化不对称有机合成(如Aldol反应、Michael加成反应、Mannich反应等)中的研究进展。     

季戊四醇衍生物为骨架的糖簇、糖树枝状分子的合成与应用

综述了以季戊四醇衍生物为骨架的糖簇、糖树枝状分子的合成与应用. 由于季戊四醇衍生物本身所具备的结构特点, 这类分子非常适合于合成新型的糖簇分子和糖树枝状分子. 同时, 由于季戊四醇衍生物在有机合成领域应用广泛, 很多有机合成方法都可以应用到这类糖缀合物的合成中.     

New methodology for acridine synthesis using a rhodium-catalyzed benzannulation

A new methodology for the synthesis of acridine derivatives is disclosed. The starting materials are commercially available quinolines, which can be converted, via five high efficient steps, in a key quinoline intermediate substituted with a TBS-protected-enol-ether and an internal alkyne. The key and last step is a rhodium-catalyzed benzannulation of the quinoline intermediate yielding the desired poly-substituted acridines derivatives.     

Scope and limitations of a new highly selective synthesis of unsymmetrical monomers for the synthesis of precursors toward poly(arylenevinylene)s

In our laboratory a precursor route to poly(p-phenylenevinylene) derivatives is developed in which unsymmetrically substituted p-xylene derivatives, possessing a benzylic sulfinylalkyl group, are used as monomers. Because of this unsymmetry, we were forced to investigate thoroughly the synthesis of these sulfoxides, as we start from symmetric and readily accessible molecules, namely, bis(halomethyl)-p-xylene derivatives. In a former publication, a new extremely effective route for the production of these unsymmetrically substituted sulfinyl monomers was presented. This paper expands upon these previously reported results. To examine the scope and limitations of this elegant route, this new method was applied to the synthesis of various derivatives not included in the initial work.