高氯酸镁在有机合成中的应用

从有机合成化学的角度,按反应类型综述了高氯酸镁作为Lewis酸催化剂在有机化学中的应用.结果表明高氯酸镁在多种有机反应中表现出非常好的催化性能,其催化反应主要涉及保护基团的形成和裂解、氧化和还原反应、成环反应、加成反应、取代反应和重排反应等.     

Carbon-Carbon Bond Formation Reactions in the Preparation of Hydrindanones

1 Introduction Carbon-carbon bond formation reactions are highly important in organic chemistry, because these reactions may be used to construct complicated molecules. Samarium diiodide is known to be a one-electron reducing agent and recently used in many organic reactions. A radicals is postulated as an intermediate, which may be formed by direct reduction of halides, carbonyls and other functional groups.1IntroductionCarbon-carbon bond formation reactions are highly i mportant in organic …     

Recent developments in homobimetallic reagents and catalysts for organic synthesis

Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as catalysts.They can be classified according to the number of metals they contain.Bimetallic compounds are important organometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or different.In this paper,we focus on homobimetallic compounds.Homobimetallic compounds are generally used as dianions to react with electrophiles in organic synthesis.Recently,homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions.     

煤热解过程中二次反应作用建模

为了弥补实验方法在研究煤热解中二次反应机理的不足,基于单体结构、碎片断裂、官能团理论和化学反应原理,建立了改进的煤粉热解模型。该模型可以由煤粉特性、反应条件预测热解产物产率及释放过程,将挥发份释放的模拟结果与一些实验结果比较,吻合较好。在此模型基础上,研究产物释放随终温的变化及二次反应的作用。结果表明:反应终温升高挥发份产率的增加主要来源于轻质气体的增加。一次反应气体产物的二次反应对热解过程有抑制作用,随着反应进行,由于化学反应平衡的移动,该抑制作用减弱,通过化学平衡原理分析了该作用的机理。     

过热水中的有机反应

过热水在有机反应中有特殊的应用。在一定的温度和压力下，水成为一种高效的有机反应的介质，在反应中充当反应物、溶剂、催化剂等角色，对很多有机反应来说，既可以提高反应速度，又可以提高其反应的化学选择性。对过热水的研究已成为有机化学中很有潜力的一个分支－－水化学。     

Mandelate racemase and muconate lactonizing enzyme are mechanistically distinct and structurally homologous

Mandelate racemase (MR) and muconate lactonizing enzyme (MLE) catalyse separate and mechanistically distinct reactions necessary for the catabolism of aromatic acids by Pseudomonas putida. The X-ray crystal structure of MR, solved at 2.5 A resolution, reveals that the secondary, tertiary and quaternary structures of MR and MLE are remarkably similar; also, MR and MLE are about 26% identical in primary structure. However, MR has no detectable MLE activity and vice versa. Thus, MR and MLE constitute the first example of enzymes that catalyse different reactions, as opposed to mechanistically identical reactions on different substrates, yet possess sufficient structural and sequence identity that they are likely to have evolved from a common ancestor. The discovery that MR and MLE catalyse different reactions but share a common structural framework has broad implications for the natural evolution of enzymes and metabolic pathways, as well as for the rational modification of enzyme activities.     

一氧化氮的生理化学与炎症

目前,关于一氧化氮(NO)在炎症中的作用说法不一,甚至矛盾。有的认为NO具有强烈的抗炎症作用,而有的却认为NO可促进炎症引起的细胞和组织功能障碍。阐明NO的生理化学(physi-ologicalchemistry)将有利于弄清和区别NO各种生物学效应的机制。NO的生理化学包括直接和间接的二种反应。直接反应是NO与一个生物分子或有关靶的直接作用,它在NO呈低速率产生时发生,起着正常生理条件下的调节性和抗炎症效应。间接反应是由NO形成的中间调节物,如NO和氧或超氧起反应衍生的活性氧化氮引起的反应,它在NO产生加快时发生,起促炎症效应。     

Recent progress in lanthanide-catalyzed organic reactions in protic media

Lanthanide triflates are stable in water. It is possible for lanthanides to undergo many organic reactions in environmentally friendly solvents. This makes lanthanides very promising in the field of green chemistry. This review describes the recent development of the lanthanidecatalyzed organic reactions in protic solvents. Those reactions include Diels-Alder, Aldol, Allylation, acetalization, pericyclization, radical reactions as well as some newlydeveloped lanthnidesbased catalysts.     

3-RPS并联机构的主动力和约束力分析

对3-RPS并联机构进行了动力分析.首先,通过列出所有构件的力和力矩平衡方程确定驱动力和平台受到的约束反力,即3-RPS机构的球副反力.当主动力和球副反力得到,其它约束力就迎刃而解.本文给出了2个数值算例,求出了主动力和全部运动副的约束反力.并通过此例讨论这种方法的优缺点和将来的发展.     

H_2S和CH_3SH与硅锡烯加成反应的理论研究

采用密度泛函理论方法研究了H2S及CH3SH与硅锡烯的加成反应的微观机理和势能剖面.计算结果表明,所研究反应由多步机理组成且反应的初始步骤为H2S或CH3SH对硅锡烯的亲核进攻.反应过程中Si(Sn)-S键总是先于Sn(Si)-H键形成.形成Si-S键的反应在动力学上比形成Sn-S键的反应有利,且主要由能量因素决定.CH3SH作为亲核反应试剂比H2S更活泼.     

Control of four stereocentres in a triple cascade organocatalytic reaction

Efficient and elegant syntheses of complex organic molecules with multiple stereogenic centres continue to be important in both academic and industrial laboratories. In particular, catalytic asymmetric multi-component 'domino' reactions, used during total syntheses of natural products and synthetic building blocks, are highly desirable. These reactions avoid time-consuming and costly processes, including the purification of intermediates and steps involving the protection and deprotection of functional groups, and they are environmentally friendly and often proceed with excellent stereoselectivities. Therefore, the design of new catalytic and stereoselective cascade reactions is a continuing challenge at the forefront of synthetic chemistry. In addition, catalytic cascade reactions can be described as biomimetic, as they are reminiscent of tandem reactions that may occur during biosyntheses of complex natural products. Here we report the development of an asymmetric organocatalytic triple cascade reaction for the synthesis of tetra-substituted cyclohexene carbaldehydes. This three-component domino reaction proceeds by way of a catalysed Michael/Michael/aldol condensation sequence affording the products with good to moderate yields (25-58 per cent). During this sequence, four stereogenic centres are formed with high diastereoselectivity and complete enantioselectivity. In addition, variation of the starting materials can be used to obtain diverse polyfunctional cyclohexene derivatives, which can be used as building blocks in organic synthesis.     

Proline-catalysed Mannich reactions of acetaldehyde

Small organic molecules recently emerged as a third class of broadly useful asymmetric catalysts that direct reactions to yield predominantly one chiral product, complementing enzymes and metal complexes. For instance, the amino acid proline and its derivatives are useful for the catalytic activation of carbonyl compounds via nucleophilic enamine intermediates. Several important carbon-carbon bond-forming reactions, including the Mannich reaction, have been developed using this approach, all of which are useful for making chiral, biologically relevant compounds. Remarkably, despite attempts, the simplest of all nucleophiles, acetaldehyde, could not be used in this way. Here we show that acetaldehyde is a powerful nucleophile in asymmetric, proline-catalysed Mannich reactions with N-tert-butoxycarbonyl (N-Boc)-imines, yielding beta-amino aldehydes with extremely high enantioselectivities-desirable products as drug intermediates and in the synthesis of other biologically active molecules. Although acetaldehyde has been used as a nucleophile in reactions with biological catalysts such as aldolases and thiamine-dependent enzymes, and has also been employed indirectly, its use as an inexpensive and versatile two-carbon nucleophile in asymmetric, small-molecule catalysis will find many practical applications.     

Carbon-heteroatom bond formation catalysed by organometallic complexes

At one time the synthetic chemist's last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal-heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future.     

航海环境下军人不良心理反应的影响因素及干预措施分析

时航海环境下军人的不良心理反应、影响因素以及干预措施进行了分析。认为不良心理反应从轻到重表现为心理应激反应、人格变化、心理疾病,不良心理反应的产生与海上及舰艇生活环境、人格因素、舰艇人际环境、工作任务等因素有关。从改善航海生活工作环境、加强心理训练、建立科学的轮班作息制度以及开展心理疏导和咨询等几个方面探讨了海上心理应激反应的干预措施。     

锗硅烯与H_2O加成反应的计算研究

采用密度泛函理论方法研究了两种锗硅烯(H2Ge=Si H2及Ph2Ge=Si Ph2)与H2O的加成反应的微观机理和势能剖面,分析了加成反应中区域选择性的起源.计算结果表明,H2O的单聚体、二聚体及三聚体均可作为亲核试剂与锗硅烯发生加成反应.形成Si—O键和Ge—O键的反应均为复杂反应,且Si(Ge)—O键比Ge(Si)—H键优先形成.加成反应的区域选择性由动力学因素决定.H2O作为亲核试剂的反应活性低于CH3OH.     

沉缸酒老熟化的机理研究

沉缸酒在发酵过程中，发生了一系列复杂的物理化学变化，如氧化、还原、酯化、缔合等，同时伴随着色泽、成分的变化及分子缔合作用．这些变化是酒的口感变绵软醇和的重要原因．从反应机理的角度对这些变化过程进行了深入研究．     

中药方剂中乳香类药物不良反应分析及临床对策

 乳香可舒筋行气,活血化瘀,是中医治疗痹症、湿阻病等多种疾病的常用药材,但乳香类药物存在诱发不良反应的风险。通过回顾性研究,将2022年1—6月于北京中医药大学附属护国寺中医医院开具含有乳香成分的中药处方作为研究对象,通过统计描述、相关性分析及多因素回归分析,旨在明确影响乳香不良反应的独立性因素。采用的指标包括处方中的乳香剂量、给药方式,患者的年龄、性别、过敏史以及记录不良反应类型等。结果共纳入108例处方,其中7例处方引发了不良反应,包括皮肤过敏6例、腹泻1例,多因素回归分析显示患者既往过敏史是影响乳香不良反应的唯一独立危险因素;说明现阶段中医临床实践使用的含有乳香的中药方剂所致的不良反应仅与既往过敏史有关,患者过敏史是合理用药、控制不良反应中需重点把握的环节。     

The stereochemical course of amino acid activation by methionyl- and tyrosyl-tRNA synthetases.

Stereochemical analysis has long been recognised as a powerful tool for elucidating the mechanisms of chemical and enzyme-catalysed reactions. Although much is known about the stereochemical course of reactions at saturated carbon, phosphate and thiophosphate esters whose ligands to phosphorus are also tetrahedrally disposed, are capable in principle of revealing sterochemical information about events at the active site of enzymes that transform such substrates. Nucleotidyl transferases are a group of enzymes which in general selectively use one of the diastereoisomers of a nucleoside 5'(1-thiotriphosphate), such as isomers A and B of adenosine 5'(1-thiotriphosphate), designated ATP alpha S-A and ATP alpha S-B, and allow investigation of the stereochemical course of nucleotidyl transfer. We have developed a simple method based on 31P nuclear magnetic resonance spectroscopy for determining the stereochemical course of these reactions, and using this method show here that the nucleotidyl transfer step in two aminoacyl-tRNA synthetases from Escherichia coli occurs with inversion of configuration at phosphorus. These observations greatly constrain the mechanistic possibilities for these enzymes, and are interpreted most simply as a direct 'in line' transfer from ATP to the amino acid.     

Titan大气中可能生成NH3的几个反应的量子力学计算

运用耦合簇理论CCSD方法和全组态CBS-Q理论对文献（Planet Space Sci，2003，51：1003-1011．）提出的Titan大气中可能生成NH3的6个链式反应进行了热化学计算和分析．发现：（a）反应（4）-（6）在Titan环境中反应能够正向进行，具有较大的自发反应趋势，反应（2）和（3）不具有反应自发性，在低温下自发反应可能性更低；（b）反应（2）的转变温度为955．14K，高于这个温度反应才有可能正向进行；（c）可以认为这6个链式反应在Titan大气的低温环境中自然合成NH3是不太可能的；（d）耦合簇理论CCSD方法和全组态CBS-Q理论的计算结果相吻合，互相印证了结论的可靠性．     

SO_2与二烯烃的光化学反应

用ＧＣ和ＧＣ／ＭＳ法研究了ＳＯ＿２，与１，３－丁二烯和１，３－戊二烯在无氧以及有氧体系中的光化学反应。确定了主要反应物，研究了体系的动力学，探讨了部分产物的生成机制。