Recent advances in the activation of boron and silicon reagents for stereocontrolled allylation reactions

Despite the popularity of boron and silicon allylation reagents in stereocontrolled synthesis, they suffer from a number of inherent limitations that have slowed down their development as synthetic tools for nucleophilic additions to carbonyl compounds and imine derivatives. These limitations are the low reactivity and diastereoselectivity of allyl trialkylsilane reagents, and the lack of catalytic systems for the activation and substoichiometric control of enantioselectivity in the additions of allyl boron reagents. To develop more efficient and general methods for the control of absolute stereochemistry in the resulting homoallylic alcohols, new approaches aimed at solving the problem of activation of allylic boron and silicon reagents are needed. This Minireview describes a number of recent approaches that have been devised to address this problem.     

DETERMINATION OF DEGREE OF CRYSTALLINITY OF NYLON 1212 BY WIDE-ANGLE X-RAY DIFFRACTION

Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WAXD method is compatible with those obtained by density and calorimetry methods.     

Iridium mediated methyl and phenyl C-H activation of 2-(arylazo)phenols. Synthesis, structure, and spectral and electrochemical properties of some organoiridium complexes

Reaction of 2-(2′,6′-dimethylphenylazo)-4-methylphenol with [Ir(PPh₃)₃Cl] in refluxing ethanol in the presence of a base (NEt₃) affords an organoiridium complex 5, where the 2-(2′,6′-dimethylphenylazo)-4-methylphenol is coordinated to iridium, via C-H activation of a methyl group, as a dianionic tridentate C,N,O-donor. Two triphenylphosphines and a hydride are also coordinated to the metal center. A similar reaction carried out in toluene affords complex 5 along with a similar complex 7, where a chloride is coordinated to iridium instead of the hydride. Reaction of 2-(2′-methylphenylazo)-4-methylphenol with [Ir(PPh₃)₃Cl] in refluxing ethanol in the presence of a base (NEt₃) affords an organoiridium complex 12, where the 2-(2′-methylphenylazo)-4-methylphenol is coordinated to iridium, via C-H activation at the ortho position of the phenyl group in the 2′-methylphenylazo fragment, as a dianionic tridentate C,N,O-donor. Two triphenylphosphines and a hydride are also coordinated to the metal center. A similar reaction carried out in toluene affords a complex 12 along with a similar complex 13, where a chloride is coordinated to iridium instead of the hydride. Structures of complexes 5, 12 and 13 have been determined by X-ray crystallography. In all these complexes, the two triphenylphosphines are trans. All these complexes show intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows an Ir(III)-Ir(IV) oxidation within 0.60-0.73 V vs. SCE, followed by an oxidation of the coordinated 2-(arylazo)phenolate ligand within 1.08-1.39 V vs. SCE. A reduction of the coordinated 2-(arylazo)phenolate ligand is observed within −1.10 to −1.26 V vs. SCE.     

部分水解聚丙烯酰胺在多孔介质中的静态吸附研究——水解度对吸附量的影响

部分水解聚丙烯酰胺在多孔介质中的静态吸附研究———水解度对吸附量的影响杨继萍李惠生黄鹏程（北京理工大学化工与材料学院北京１０００８１）（北京航空航天大学材料科学与工程系北京１０００８３）关键词部分水解聚丙烯酰胺，水解度，多孔介质，静态吸附聚合物作为...     

What theoretical and/or chemical significance is to be attached to the magnitude of an activation energy determined for a solid-state decomposition?

This critical survey argues that the theory, conventionally used to interpret kinetic data measured for thermal reactions of initially solid reactants, is not always suitable for elucidating reaction chemistry and mechanisms or for identifying reactivity controls. Studies of solid-state decompositions published before the 1960s usually portrayed the reaction rate as determined by Arrhenius type models closely related to those formulated for homogeneous rate processes, though scientific justifications for these parallels remained incompletely established. Since the 1960s, when thermal analysis techniques were developed, studies of solid-state decompositions contributed to establishment of the new experimental techniques, but research interest became redirected towards increasing the capabilities of automated equipment to collect, to store and later to analyze rate changes for selected reactions. Subsequently, much less attention has been directed towards chemical features of the rate processes studied, which have included a range of reactants that is much more diverse than the simple solid-state reactions with which early thermokinetic studies were principally concerned. Moreover, the theory applied to these various reactants does not recognize the possible complexities of behaviour that may include mechanisms involving melting and/or concurrent/consecutive reactions, etc. The situation that has arisen following, and attributable to, the eclipse of solid-state decomposition studies by thermal analysis, is presented here and the consequences critically discussed in a historical context. It is concluded that methods currently used for kinetic and mechanistic investigations of all types of thermal reactions indiscriminately considered by the same, but inadequate theory, are unsatisfactory. Urgent and fundamental reappraisal of the theoretical foundations of thermokinetic chemical studies is now necessary and overdue. While there are important, but hitherto unrecognized, delusions in thermokinetic methods and theories, an alternative theoretical explanation that accounts for many physical and chemical features of crystolysis reactions has been proposed. However, this novel but general model for the thermal behaviour and properties of solids has similarly remained ignored by the thermoanalytical community. The objective of this article is to emphasize the now pressing necessity for an open debate between these unreconciled opinions of different groups of researchers. The ethos of science is that disagreement between rival theories can be resolved by experiment and/or discussion, which may also strengthen the foundations of the subject in the process. As pointed out below, during recent years there has been no movement towards attempting to resolve some fundamental differences of opinion in a field that lacks an adequate theory. This should be unacceptable to all concerned. Here some criticisms are made of specific features of the alternative reaction models available with the stated intention of provoking a debate that might lead to identification of the significant differences between the currently irreconciled views. This could, of course, attract the displeasure of both sides, who will probably criticise me severely. Because I intend to retire completely from this field soon, it does not matter to me if I am considered to be ‘wrong’, if it contributes to us all eventually agreeing to get the science ‘right’.     

多肽合成中羧基活化方法的一些新进展

本文简要叙述了多肽合成中的羧基活化问题。重点讨论了作者近年来在此领域所进行的工作,如含氮杂环作为活化羧基的离去基团和几个新的含磷多肽试剂。     

拟合粘度曲线法研究高聚物的长链支化

本文介绍了用计算机试误法拟合粘度曲线,讨论支化参数的方法,本法可以同时确定支化临界分子量和支化程度,在此基础上可以同时得到支化参数及平均分子量、分子量分布.以聚乙烯标准参考物:SRM 1475(线型)、1476(支化物)及镍催化顺式聚丁二烯为对象介绍了上述方法.     

Effective synthesis of 5-aryl-3-ethylidene-3H-pyrrol-2-ones

Substituted 5-aryl-3-ethylidene-3H-pyrrol-2-ones were synthesized by the reaction of the corresponding 4-aryl-4-oxobutanoic acids with ketones in the presence of aminating agents. The conditions of this reaction were developed with the use of both the conventional condensation technique and microwave activation. The structures of the reaction products were con-firmed by elemental analysis, IR spectroscopy, and ¹H NMR spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 693–696, April, 2006.     

碳氟醇与阴离子表面活性剂的相互作用

测定了不同比例的C_(10)_H_(21)SO_4Na-C_3F_7CH_2OH、C_7F_(15)COONa-C_3H_7CH_2OH混合水溶液的表面张力,加入C_3F_7CH_2OH可增加阴离子表面活性剂的表面活性;在表面层中,C_3F_7CH_2OH与C_(10)H_(21)SO_4Na间分子相互作用比C_3F_7CH_2OH-C_7F_(15)COONa体系弱;这是由于CF链与CH链间“互疏”作用的结果;随着C_3F_7CH_2OH浓度增加,对C_(10)H_(21)SO_4Na胶团反离子结合度也随之增加。     

铈离子与氨基甲酸酯类化合物引发丙烯酰胺聚合的研究

本文对铈离子与苯基氨基甲酸酯类化合物在H_2O-CH_3CN(3∶1,V/V)及H_2O-HCONH_2(1∶2,V/V)两种介质中引发丙烯酰胺的聚合进行了研究。考察了不同结构的苯基氨基甲酸酯对聚合的影响。苯基氨基甲酸酯类化合物对铈离子引发聚合均有促进作用,其中对-甲苯基氨基甲酸酯的促进作用最为显著。测定了聚合反应表现活化能及聚合动力学方程,并提出了聚合反应机理。