绿色合成--21世纪的有机合成

绿色合成,作为当代有机合成发展的一个重要学科前沿,已成为化学发展的一个方向.从催化剂、绿色溶剂、合成手段、合成方法、计算机辅助绿色合成等方面综述了近年来国内外实现绿色合成的有效途径,并对绿色合成的目标进行了探讨.参考文献35篇.     

不对称合成α-氮杂环丁酮的研究进展

α-氮杂环丁酮是合成培南类抗生素的母核. 作为一类具有生物活性化合物合成子的使用, 促进了其合成方法的研究. 综述了不对称合成氮杂环丁酮的研究进展, 详细讨论了氮杂环丁酮的合成方法.     

微波辅助晶化法合成MCM-22分子筛的研究

开展了微波辅助法合成MCM-22分子筛的研究, 经过29 h微波晶化得到了与传统水热法合成5 d相同的100%晶化的样品, 有效地缩短了合成时间. 通过XRD, SEM, FT-IR, ICP和²⁷Al MAS NMR技术表征, 微波辅助合成样品具有高纯度、均一形貌, Al原子有效进入骨架等特征. 对合成中的关键性条件, 如结构导向剂的含量进行了深入研究, 并给出了可能的合成机理. 此外, 通过在合成液中添加少量高介电损失物质, 进一步缩短了合成时间.     

咪唑及其衍生物的合成研究进展

咪唑及其衍生物作为药物中间体,在生物学、医学、有机化学中占据重要位置.目前咪唑的合成方法主要包括Radziszewski法、Phillips法、溴乙醛法.咪唑衍生物的合成方法主要包括金属催化剂合成法、酸性催化剂合成法、离子液体催化剂合成法等.本文对咪唑及其衍生物的合成方法进行了总结与归纳,并阐述了各种方法的优缺点.     

Fischer吲哚合成法的研究进展

吲哚及其衍生物具有某些生物活性, 其合成方法很多. 其中Fischer吲哚合成是最便捷和经济的合成方法, 应用最多. 对此法近十年来的合成工艺进行了综述和评价.     

添加碳元素合成化学计量比LiNiO2

本文采用添加碳元素、葡萄糖及使用多种试剂为原料的合成方法,合成了具有化学计量比的LiNiO2.分析了这些方法在合成反应中的作用,同时给出了合成LiNiO2的最佳反应条件.     

微波加热合成含有极少量非分子筛缺陷孔的LTA型分子筛膜

 以改进的原位合成路线,于管状氧化铝载体上合成了高性能的LTA型分子筛膜. 考察了常规加热和微波加热对合成的影响. 对于95%的异丙醇原料液,常规加热合成和微波加热合成的分子筛膜表现出了相似的优良性能. 但是,当原料液中的水含量低于2.0%时,常规加热合成的分子筛膜不再具有有效的脱水性能,这是由于其膜层中有相当数量的纳米级缺陷孔存在. 采用微波加热在很大程度上消除了合成过程中非分子筛缺陷孔的生成.     

中氮茚的合成研究进展

中氮茚及其衍生物的特殊结构使得它们在生物、医药等领域具有广泛的应用. 其合成方法很多, 最近大量文献报道了它们的合成. 综述了近几年来中氮茚及其衍生物的合成方法, 并展望了其今后合成发展的方向.     

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.     

苯并咪唑类化合物的合成研究进展

苯并咪唑类化合物应用广泛. 按不同的合成原料和合成方法进行分类, 综述了近年来苯并咪唑类化合物合成研究的新进展.     

Modular Synthesis of Phosphite and Phosphoramidite Ligands for Rh-Catalyzed Hydroformylation

Rhodium-catalyzed hydroformylation of olefins is an important method for synthesizing aldehydes, and it is worth noting that regioselectivity and enantioselectivity of the product controlled by ligand are the most commonly used strategies. The modular synthesis of phosphite and phosphoramidite ligands have significant advantages of simple synthesis and high catalytic activity, which was why these ligands have been widely used in hydroformylation reactions. Herein, we focus on the synthesis methods and design ideas of such ligands, as well as their application effects in hydroformylation reactions. This review aims to provide a reference for the design and synthesis of ligands in hydroformylation subsequently.     

手性螺环配体的合成及其在不对称催化反应中的应用研究进展

手性螺环配体的合成及其在不对称催化反应中的应用是不对称合成和催化研究中重要的研究领域之一, 一些手性螺环配体被合成出来并成功地应用于不对称催化反应中. 综述了近十年来手性螺环配体的合成及在不对称催化反应中的应用研究进展.     

Ruthenium Olefin Metathesis Catalysts Featuring N-Heterocyclic Carbene Ligands Tagged with Isonicotinic and 4-(Dimethylamino)benzoic Acid Rests: Evaluation of a Modular Synthetic Strategy

A modular and flexible strategy towards the synthesis of N-heterocyclic carbene (NHC) ligands bearing Brønsted base tags has been proposed and then adopted in the preparation of two tagged NHC ligands bearing rests of isonicotinic and 4-(dimethylamino)benzoic acids. Such tagged NHC ligands represent an attractive starting point for the synthesis of olefin metathesis ruthenium catalysts tagged in non-dissociating ligands. The influence of the Brønsted basic tags on the activity of such obtained olefin metathesis catalysts has been studied.     

Synthesis and coordination chemistry of macrocyclic ligands featuring NHC donor groups

Poly-NHC (NHC = N-heterocyclic carbene) ligands emerged almost immediately after the first stable NHCs had been described. Macrocyclic ligands, featuring NHC donor groups and their metal complexes, however, remained rare until recently. This perspective highlights modern developments in the fields of synthesis and coordination chemistry of macrocyclic poly-NHC ligands. These include the synthesis of tetracarbene ligands which were obtained from complexes of β-functionalized isocyanides followed by cyclization of the coordinated iscocyanide ligands to NH,NH-functionalized NHCs and the subsequent metal template controlled bridging alkylation of the NH,NH-NHCs to yield the macrocycle. The template synthesis of ligands featuring a mixed NHC/phosphine donor set like [11]ane-P(2)C(NHC) and [16]ane-P(2)C(NHC)(2) by linkage of NH,NH-NHCs to different phosphines is also presented. Finally, methods for the preparation of cyclic polyazolium salts, their deprotonation and metalation and the different modes of coordination of such macrocyclic poly-NHC ligands are discussed.     

Synthesis of non-symmetric bis(oxazoline)-containing ligands and their application in the catalytic enantioselective Nozaki-Hiyama-Kishi allylation of benzaldehyde

We report the good to high-yielding three-step synthesis of non-symmetrical bis(oxazoline)-containing ligands possessing an N-thienylaniline unit. The convergent synthesis employed a palladium-catalysed aryl amination of 2-(2'-bromothiophene)nitrile as the key step, with sixteen ligands prepared in total. These ligands were subsequently applied in the chromium-catalysed enantioselective Nozaki-Hiyama-Kishi allylation of benzaldehyde with an optimal enantioselectivity of 73%.     

New monodentate chiral phosphite ligands for asymmetric hydrogenation

We report the synthesis of new chiral monodentate phosphite ligands with a biphenyl backbone, the axial chirality of which is introduced early in the synthesis and locked by a chiral alkylenedioxy bridge. We also describe results obtained with these ligands in rhodium-catalysed asymmetric hydrogenation of various substrates.     

The synthesis of P-stereogenic MOP analogues and their use in rhodium catalysed asymmetric addition

The synthesis is reported of novel P-stereogenic binaphthyl substituted monophosphines via a short five-step synthesis using a nickel coupling reaction with separation of the borane-protected diastereomeric products. Extensive coordination studies of these ligands with a number of well-known metal precursors were performed to more effectively understand their behaviour during catalysis.These ligands and some previously reported P-stereogenic ligands were tested in the rhodium catalysed asymmetric addition of phenyl boronic acid to napthaldehyde. These studies in asymmetric catalysis were used to compare the chiral induction of ligands that combine both axial and central chirality with ligands lacking P-stereogenicity.     

过渡金属/磷配体催化不对称氢化反应研究进展

正手性过渡金属配合物催化的不对称氢化是合成手性药物、农药和精细化工中间体的重要方法.到目前为止,已经有一些过渡金属/配体配合物催化的不对称氢化反应得到工业化应用,典型的实例如孟山都公司采用手性双齿膦配体DIPAMP生产L     

手性双噁唑啉配体的合成进展

总结了近年来用于不对称催化的各种双噁唑啉配体的合成方法,包括丙二酸酯类、酒石酸类、吡啶类、联苯、联萘及二茂铁类等多种双噁唑啉配体的合成.另外,还讨论了苯甲醚类、二联苯噁二唑类、联苯胺类与氮杂类等新型双噁唑啉配体的合成.     

Solid-phase parallel synthesis of phosphite ligands

Various routes for the synthesis of polymer-bound phosphites and phosphoramidites have been investigated. In the presence of a suitable activator the supported phosphoramidites react cleanly with alcohols to give the corresponding monodentate phosphite ligands in solution. We have applied this novel solid-phase route in the parallel synthesis of several monodentate chiral and achiral phosphite ligands.