离子热法合成分子筛的研究进展

离子热法是以离子液体或低共熔混合物为介质的一种新型的分子筛合成方法, 它提供了一种离子态的独特合成环境, 为合成新型分子筛及研究分子筛的生成机理提供了机会. 本文综述了离子热法在分子筛合成方面取得的一些进展, 包括合成方法的创新、合成机理的研究、新材料的合成以及新型催化剂的制备等, 并展望了其发展前景.     

糖肽合成的新进展

本文综述了近年来在糖肽合成方面的研究进展, 主要包括三氯乙酰亚胺酯法, 缩水内醚糖法, 酶合成法, 固相合成法及酶与固相结合法。分析了不同的离去基团和不同的保护基策略对糖肽合成的影响。     

Making Solid‐Phase Peptide Synthesis Greener: A Review of the Literature

To date, the synthesis of peptides is concurrent with the production of enormous amounts of toxic waste. DMF, CH₂Cl₂, and NMP are three of the most toxic organic solvents used in chemical synthesis and are the most common solvents used for peptide synthesis. Additionally, concerns about the hepatotoxicity caused by exposure to DMF and from the toxic and allergenic nature of additives used in peptide synthesis necessitates the need for a green, environmentally friendly, and safer protocol for peptide synthesis. This review summarizes the current literature on green solid‐phase peptide synthesis successes and challenges encountered. The review concludes with suggestions for future research towards a simple and efficient green peptide synthesis protocol.     

Wallichanol类天然产物ABC环系合成研究

Wallichanol是一类具有独特桥环结构的二萜天然产物.以2-甲基-1,3-环己二酮作为起始原料,通过高立体选择性的Diels-Alder反应和金催化的炔烃碳环化反应构建Wallichanol的ABC三环核心骨架,共七步路线,总收率为42%.该合成工作为Wallichanol类天然产物全合成奠定了研究基础.     

Synthesis of eudistomin C and E: improved preparation of the indole unit

An improved synthesis of the indole unit, a key intermediate for eudistomin C, was established utilizing Makosza's indole synthesis. A concise total synthesis of eudistomin E was achieved on the basis of the improved synthesis.     

绿色路易斯酸三卤化铟在有机合成中的应用

三卤化铟作为温和的路易斯酸可在水、醇等绿色溶剂中实现高化学选择性、高 区域选择性和高立体选择性的化学转化。综述了三卤化铟在羟醛反应和类羟醛-曼 尼希反应、Fiedel-Crafts反应、环氧化合物的重排反应、α-氨基膦酸的合成、喹 啉环系的构建、酯交换反应、Diels-Alder反应和杂Diels-Alder反应,手性呋喃二 醇的合成、水相中的叠氮解反应和二硫缩醛的制备中的应用,同时还总结了本课题 组将三卤化铟应用于Biginelli反应和还原脱氧反应的反应结果。三卤化铟在有机 合成中潜在的优势将推动“绿色化学”的发展。     

A metalation strategy for the construction of functionalized naphthalenes: the first synthesis of guieranone A

The first synthesis of the natural product guieranone A is described, demonstrating a one-pot procedure for the synthesis of protected-1,3,6,8-tetraoxygenated naphthalenes and a subsequent directed metalation synthesis of 2-keto naphthalenes.     

meso Compounds: Stepchildren or Favored Children of Stereoselective Synthesis?

After more than a quarter of a century of development, the methodology of stereoselective synthesis appears to be fully matured. In line with this, the potential that meso compounds offer in stereoselective synthesis is clearly recognized. The use of meso compounds in synthesis is, however, in no way commensurate with this potential, because, ironically, the synthesis of meso compounds in the first place is a problem of stereoselective synthesis. Present-day methodology does not provide many useful solutions to this problem. This Review therefore addresses the strategies available for the synthesis of more elaborate meso compounds whose stereogenic centers have a distance >1,4 between them. meso Compounds with more than four stereogenic centers are also considered. The criteria used in choosing from several strategies in the synthesis of such compounds are discussed.     

Total synthesis of ionomycin using ring-opening strategies

[structure: see text] The total synthesis of the polyether antibiotic ionomycin, a calcium ionophore, is described. The synthesis demonstrates the utility of ring-opening methodologies as applied to the synthesis of polypropionate and deoxypolypropionate subunits, which are found in two of the four fragments in the synthesis.     

RNA synthesis via dimer and trimer phosphoramidite block coupling

The solid-phase synthesis of oligoribonucleotides using dimer and trimer phosphoramidite blocks is described. This method significantly reduces the total number of steps required in the synthesis of a target RNA sequence, provides more material, and simplifies separation of the product from shorter failure sequences. The procedure is illustrated by the synthesis of UpU, ApA, and UpUpU phosphoramidite blocks and their use in the rapid synthesis of oligoribonucleotides on a solid support. Dimer and trimer amidite blocks will likely find use in the large scale solution (or solid)-phase synthesis of siRNA drugs.     

有机合成光化学及其研究现状

光化学合成在有机合成化学,特别在一些非常见结构的合成中占有特殊的地位,能大大缩短传统合成化学的步骤而经济实用.本文主要以天然产物及其中间体的合成,举例介绍有机合成光化学及其研究现状.     

Metal catalysts: applications in higher-membered <Emphasis Type="Italic">N</Emphasis>-heterocycles synthesis

In recent decades, a large number of reports related to synthesis of N-, O- and S-containing heterocycles have appeared owing to a wide variety of their biological activity. The metal-catalyzed synthesis of heterocycles is becoming an important and highly rewarding protocol in organic synthesis. This review focuses on the use of metal as a catalyst for the synthesis of nitrogen-containing heterocycles. It describes the formation of higher-membered heterocyclic rings.     

A stereoselective synthesis of (+)-herboxidiene/GEX1A

A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.     

High pressure synthesis of polyimides and related polymers

This paper reviews our current studies on the high pressure synthesis of polyimides and related condensation polymers. After a brief introduction of the solid-state thermal synthesis of polyimides starting from nylon-salt-type monomers, the paper deals with the high pressure synthesis of polyimides, the preparation of polyimide-silica hybrid materials by the combination of the above synthetic method for polyimides and the sol-gel reaction for silica synthesis, and the high pressure synthesis of polybenzoxazoles and addition-type polyaminoimide.     

Rapid synthesis of gold nanorods using a one-step photochemical strategy

Rapid synthesis of gold nanorods of controlled dimensions is one of the desired aspects of nanotechnology as a result of the potential of these nanomaterials for biomedical applications. The synthesis of gold nanorods has been achieved using a photoinitiator as an instant source of ketyl radicals, which allows the synthesis of gold nanorods in minutes. This is the first report providing a one-step synthesis of nanorods of controlled dimensions in 20-30 min using photoinitiator I-2959 as a source of ketyl radicals. Furthermore, the role of UV intensity, the concentration of silver ions, and the presence of cosolvents and a cosurfactant have been studied in detail in an effort to produce nanorods with controlled dimensions in higher yields. The role of acetone in nanorod synthesis has been explored in detail, and it has been demonstrated that, for the photochemical synthesis of nanorods using a photoinitiator, acetone is not a critical component and can be replaced by other water-miscible solvents, thus the successful synthesis of nanorods in tetrahydrofuran (THF) has been demonstrated. It has also been found that a cosurfactant and an organic solvent are not required for the synthesis of nanorods; however, their presence is found to improve the monodispersity of nanorod samples, in addition to providing a higher yield.     

Hot or not—the influence of elevated temperature and microwave irradiation on the solid phase synthesis of an affibody

Despite the advances of solid phase peptide synthesis (SPPS) the synthesis of long peptides is still challenging. Microwave irradiation and conventional heating are considered to improve the efficiency of SPPS. It has been shown that conventional heating and heating by microwave irradiation improves the efficiency of solid phase synthesis of peptides that are prone to aggregation as compared to the synthesis at room temperature. In this Letter, the influence of elevated temperature and microwave irradiation on the homogeneity of the synthesis product of a 58-mer peptide affibody has been compared. A detailed analysis by high resolution HPLC and LC-MS mass spectrometry using a high-mass resolution Orbitrap Exactive mass spectrometer was performed. This study revealed that neither thermal heating nor microwave heating improves the yield and purity of the crude product as compared to the synthesis at room temperature. In contrast, the formation of undesirable side products rather increased by microwave irradiation. These results indicate that neither heating nor microwave enhancement of solid phase synthesis does allow a significant improvement of peptide sequences with a low aggregation potential.     

The first total synthesis of +-ratjadone

The first total synthesis of ratjadone was achieved using a highly convergent approach joining three subunits together with a Wittig olefination and a selective Heck reaction as the pivotal steps. Besides establishing a robust and reliable route for the synthesis of this orphan ligand, the configuration of unknown stereocenters could also be determined. This synthesis not only provides an additional access to a biologically important compound but also enables the synthesis of structural analogues for biological target identification.     

Light-mediated inhibition of protein synthesis

The regulation of protein synthesis is vital for a host of cell biological processes, but investigating roles for protein synthesis have been hindered by the inability to selectively interfere with it. To inhibit protein synthesis with spatial and temporal control, we have developed a photo-releasable anisomycin compound, N-([6-bromo-7-hydroxycoumarin-4-yl]methyloxycarbonyl)anisomycin (Bhc-Aniso), that can be removed through exposure to UV light. The area of protein synthesis inhibition can be restricted to a small light-exposed region or, potentially, the volume of two-photon excitation if a pulsed IR laser is the light source. We have tested the compound's effectiveness with an in vitro protein-translation system, CHO cells, HEK293 cells, and neurons. The photo-released anisomycin can inhibit protein synthesis in a spatially restricted manner, which will enable the specific inhibition of protein synthesis in subsets of cells with temporal and spatial precision.     

A new strategy for solid-phase depsipeptide synthesis using recoverable building blocks

The technique of choice for synthesis of small-scale depsipeptides is on a solid support. However, if expensive monomers have to be incorporated, solid-phase synthesis can quickly turn out to be unattractive because of its low atom economy. Herein, we describe a new type of recoverable and reuseable alpha-hydroxy acid building block for solid-phase synthesis and its application in the synthesis of a number of small cyclic depsipeptides. [structure: see text]     

亚砜亚胺类化合物的合成及应用研究进展

亚砜亚胺(Sulfoximine)类化合物是一类重要的杂原子取代化合物,引起了人们的广泛关注.综述了近十年来亚砜亚胺类化合物的研究进展,包括该类化合物的合成及在不对称催化领域中的应用、含有亚砜亚胺的生物活性小分子合成和天然产物全合成.并对发展趋势和应用前景做了展望.