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.     

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.     

Solid Phase Peptide Synthesis

The last two decades have been an era of rapid progress in peptide research. This era was begun by the work of Sanger on the amino acid sequence determination of insulin and by du Vigneaud on the structure determination and synthesis of oxytocin. This period has seen impressive progress in the structure elucidation and synthesis of many peptides of natural origin and of great biological significance, as well as in methods for sequence determination and chemical synthesis of peptides [1–4]. Perfection of techniques and instruments for automatic determination of the amino acid sequence of peptides and proteins has made possible a greatly broadened understanding of genetics and evolution as well as the more chemical areas of mechanism of action of enzymes and hormones, and physical chemistry of peptides and proteins. Effective methods of peptide synthesis are crucial to progress in this area, because only by synthesis can adequate amounts of important peptides be made available for chemical, biological, and physical studies, as well as for exploration of the structure-function aspects of biological molecules. In general, progress in peptide synthesis has lagged far behind that in amino acid sequence determination. This is not surprising since effective peptide synthesis requires a very sophisticated system of selectively removable protecting groups for functions of the amino acids involved, and the synthesis of a large heteropolytner of defined sequence requires near perfection of each one of the many steps of the assembly. The classical approach to peptide synthesis, using standard organic chemical methods of synthesis and purification of intermediates, has yielded impressive results during these two decades. However, the special problems associated with the assembly of large molecules make staggering investments in time and materials necessary for the synthesis of large peptides or proteins by classical methods.     

费托合成鼓泡浆态床反应器模型化研究

建立了费托合成鼓泡浆态床反应器双泡模型,通过模型对比的方法模拟讨论了多个反应器模型,双泡模型、全混模型以及多级串联模型,对比模拟讨论了费托合成反应各模型的适用性。模拟结果说明,全混模型适用于费托合成动力学行为的考察模拟;多级串联模型在一定的级数下能够近似模拟鼓泡浆态床中费托合成反应结果,更适用于探讨返混对费托合成反应行为的影响;双泡模型能够描述鼓泡浆态床中流体力学对反应的影响。     

N-to-C solid-phase peptide and peptide trifluoromethylketone synthesis using amino acid tert-butyl esters

Solid-phase peptide synthesis in the N-to-C direction, opposite to the classical C-to-N direction of peptide synthesis, provides the synthetically versatile C-terminal carboxyl group for further modification into C-terminally modified peptide mimetics. These are of general interest as potential bioactive agents, particularly as protease inhibitors. Elaboration of peptide mimetics on the solid-phase would facilitate synthesis of peptide mimetic combinatorial libraries. This report describes an effective strategy for solid-phase inverse peptide synthesis based on readily available amino acid tert-butyl esters. The potential of this approach for peptide mimetic synthesis is demonstrated by the solid-phase synthesis of two peptide trifluoromethylketones.     

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.     

Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen Using Tailored Pd Nanocatalysts: A Review of Recent Findings

Direct synthesis of hydrogen peroxide from hydrogen and oxygen is being actively studied as an alternative to the current manufacturing process. The direct synthesis route has not reached the point of commercialization because of low yields, but significant effort is being spent on enhancing the productivity. With advances in computational capacity, simulation studies based on DFT calculations now offer directions for catalyst improvement, but such modifications can only be realized through the application of nanoparticle synthesis techniques that allow for nanocrystal morphology and size control and unique immobilization. To date, there have only been a small number of studies on such nanoparticles with size and crystallographic homogeneity for the direct hydrogen peroxide synthesis. According to our knowledge no other group has systematically investigated application of nanoparticles in direct synthesis of hydrogen peroxide, and thus included in this review are primarily previous studies conducted by our group. In this review, we discuss the utilization of nanotechnology for the synthesis of Pd catalysts and its effect on the direct synthesis of hydrogen peroxide, and we suggest a direction for future studies.     

A short enantioselective synthesis of (+)-eleutherin, (+)-allo-eleutherin and a formal synthesis of (+)-nocardione B

A short enantioselective synthesis of (+)-eleutherin, (+)-allo-eleutherin and the formal synthesis of (+)-nocardione B is described. The synthesis is completed in six steps in overall yields of 8% for eleutherin and 14% for allo-eleutherin. The synthetic strategy features an efficient combination of the Dötz annulation reaction with a chiral alkyne and an oxa-Pictet Spengler reaction as the keys steps in the stereodivergent synthesis of (+)-eleutherin and (+)-allo-eleutherin. The synthesis of (S)-(+)-2-(2′-hydroxypropyl)-5-methoxy-1,4-naphthoquinone entails the formal synthesis of (+)-nocardione B.     

介孔分子筛制备技术新进展—二次合成、超分子自组装和介孔生成剂法

具有内部介孔结构的多级孔分子筛兼具微孔分子筛和介孔材料的功能, 拥有良好的传质和催化特性. 在过去的几十年内, 介孔分子筛在催化、 吸附和分离领域发展迅速. 近年来, 新型合成方法的开发在很大程度上实现了介孔分子筛孔道结构、 组分及形貌灵活可控的调节. 本综述讨论了近期出现的多种新合成路径, 重点介绍了近期发展起来的二次合成制备低硅/铝介孔分子筛、 超分子自组装合成介孔分子筛及有机小分子原位合成介孔分子筛技术. 对这些合成技术的机理进行了讨论, 以期为介孔分子筛未来的发展提供思路. 文章的最后还讨论了不同的合成策略所面临的一些关键性挑战.     

Enantioselective total synthesis of (+)-digitoxigenin

An enantioselective total synthesis of (+)-digitoxigenin is described. This total synthesis is accomplished in a convergent manner using two chiral fragments prepared via the catalytic asymmetric intramolecular cyclopropanation and baker’s yeast mediated reduction developed by us, respectively. This convergent synthesis would be useful for preparing some new derivatives of digitoxigenin for SAR studies and could be applied for the total synthesis of other cardenolides left unprepared.     

A concise and improved synthesis of (+)-eleutherin, (+)-allo-eleutherin and a formal synthesis of (+)-nocardione B

A concise and improved stereoselective synthesis of (+)-eleutherin, (+)-allo-eleutherin and the formal synthesis of (+)-nocardione B is described. The synthesis is based on a Dötz benzannulation and an improved oxa-Pictet-Spengler cyclization as the key steps. The synthesis is achieved in six steps in overall yields of 18% for eleutherin and 20% for allo-eleutherin.     

SAPO分子筛的合成及影响因素的研究进展

本文综述了SAPO分子筛的主要合成方法,包括水热合成法、气相晶化法、液相晶化法、微波合成法、变温陈化法、超声合成法、程序升温法等方法.讨论了反应物的组成、模板剂、酸碱度、介质、晶化温度、晶化时间等因素对SAPO分子筛合成的影响.最后对SAPO分子筛合成方法进行了展望.     

Migratory hydroamination: a facile enantioselective synthesis of benzomorphans

We describe a highly efficient, general strategy for the enantioselective synthesis of benzomorphans (45-46% overall yield from commercially available material). The new synthesis demonstrates the effectiveness of an unprecedented diastereoselective cycloisomerization via migratory hydroamination and the power of palladium-catalyzed asymmetric allylic alkylation (AAA) of simple ketone enolates in the context of complex synthesis. The strategy outlined here for the enantioselective synthesis of three contiguous stereogenic centers and the novel cycloisomerization should have many applications in alkaloid synthesis.     

Synthesis of (+)‐Discodermolide by Catalytic Stereoselective Borylation Reactions

The marine natural product (+)‐discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for the alkylation of chiral enolates. Furthermore, this synthesis of discodermolide provides the first examples of the asymmetric 1,4‐diboration of dienes and borylative diene–aldehyde couplings in complex‐molecule synthesis.     

A microwave-assisted bismuth nitrate-catalyzed unique route toward 1,4-dihydropyridines

The classical Hantzsch reaction is one of the simplest and most economical methods for the synthesis of biologically important and pharmacologically useful 1,4-dihydropyridine derivatives. Bismuth nitrate pentahydrate under microwave irradiation is proven to act as a very efficient catalyst for a one-pot, three-component synthesis of 1,4-dihydropyridines in excellent yields from diverse amines/ammonium acetate, aldehydes and 1,3-dicarbonyl compounds within 1-3 min under solvent-free conditions. The present environmentally benign procedure for the synthesis of 1,4-dihydropyridines is suitable for library synthesis and it will find application in the synthesis of potent biologically active molecules. The excellent yield and extreme rapidity of the method is due to a concurrent effect of the catalyst and microwave irradiation.     

有机化学知识在高分子材料合成创新实验中的运用——分享几个实例

针对目前教学中存在的理论课程之间、实验课程与理论课程之间关联不够紧密等问题,探索了通过"知识关联"将有机化学基本知识运用到高分子材料合成创新实验中的教学思路。以新试剂合成及应用、荧光聚酯合成、聚酰胺合成、聚酯水解等为例,介绍了如何将有机化学新理论、新方法、新试剂应用于本科高分子化学和高分子材料实验教学,以及如何将有机化学的理论知识和实验手段应用于高分子材料合成教学中。实践表明:通过"知识关联",将有机化学基础理论知识和实验技能应用于高分子合成实验中可以提高学生对所学知识的理解和运用能力,增强学生的实验探索兴趣,有效改进了高分子材料合成实验教学的课堂气氛。     

无机纳米材料的光化学合成

无机纳米材料的合成是纳米科学发展的前提和基础之一。区别于传统的高温湿化学合成法,光化学方法在无机纳米材料的合成中表现出许多优点,并在近年来受到了广泛关注。本文分三个部分综述了近年来光化学方法在无机纳米材料合成中的应用,具体包括贵金属纳米材料的光化学合成与负载,半导体纳米材料的光化学合成以及表面等离子体共振诱导的各向异性金属纳米晶合成。最后,在总结光化学方法在无机纳米材料合成中体现出的优势及目前研究仍存在不足的基础上,我们对其未来可能的发展方向进行了展望。     

A direct route to angularly substituted hydrindanes. Formal synthesis of bakkenolide-A and synthesis of an advanced intermediate to umbellactal

A direct route for the synthesis of highly functionalized angularly substituted hydrindanes has been developed. The key step involves RO-RCM of an appropriately functionalized norbornene derivative. The hydrindane derivative obtained in this way has been used to accomplish a formal synthesis of bakkenolide-A. This protocol has also been extended for the synthesis of an advanced intermediate to the synthesis of the diterpene umbellactal.     

氧载体的氧物种直接氧化甲烷制合成气

甲烷部分氧化制合成气由于合成气中n(H2)/n(CO)接近2,可直接用于甲醇合成或烃类F-T合成等后续工业过程而在国内外受到了广泛的关注。利用氧载体的氧物种在无气相氧下直接选择氧化甲烷制合成气是天然气化工利用的新方法,本文介绍了该方法的基本原理、概念工艺和对氧载体的性能要求,对应用于该方法的铈基复合氧化物的掺杂和助剂对选择氧化甲烷性能的影响、钙钛矿氧化物氧载体的氧缺陷、氧物种迁移、结构稳定性及其氧物种氧化甲烷的性能进行了阐述和分析,提出了控制氧载体表面状态是获得高合成气选择性的关键,并对该技术今后的研究重点进行了展望。     

(R)-α-硫辛酸合成方法的研究进展

(R)-α-硫辛酸可用于预防和治疗糖尿病及相关并发症,也可以作为保健品使用,用途广泛,因而其高效合成方法长期以来受到广泛关注。 目前,合成(R)-α-硫辛酸的方法主要有酶和化学方法催化的不对称合成、消旋体的手性拆分以及手性底物控制的不对称合成。 本文将以此为分类标准,对目前所报道的(R)-α-硫辛酸合成方法进行总结归纳和展望。