环丙烷化反应中催化剂固载化的研究进展

总结了近年来关于环丙烷化反应中催化剂固载化的研究进展,包括非手性催化剂与手性催化剂的固载化,其中手性催化剂的固载化包括Schiff碱-铜、手性卟啉-钌、吡咯烷酮羧酸酯-铑、吡咯烷-金属、双唑啉-金属及手性二磺胺等催化剂的固载化.另外,还讨论了离子液体与氟两相体系在该领域的应用研究.     

C2型轴对称手性双恶唑啉的合成及其应用研究

本文综述了手性双恶唑啉的合成及其金属配合物作为手性催化剂在催化不对称反应中的应用研究进展。     

C2型轴对称手性双噁唑啉的合成及其应用研究

本文综述了手性双恶唑啉的合成及其金属配合物作为手性催化剂在催化不对称反应中的应用研究进展。     

手性咪唑啉酮类有机催化剂催化的不对称反应

近年来,不对称有机催化过程日趋成熟,用于越来越多的实际应用。相对于金属催化过程有机胺催化剂具有许多潜在的优势：相对比较稳定,价格较低,容易得到,没有金属泄露到环境或产品中的风险以及对操作环境要求不高等,有机胺催化已被证明是实现不对称转化的有效手段。手性咪唑啉酮催化剂是有机胺催化剂中重要的一种类型。本文总结了手性咪唑啉酮催化剂在Diels-Alder反应、1,3-偶极环加成、Michael反应、Friedel-Crafts烷基化等不对称催化反应中的应用研究进展,并对未来手性咪唑啉酮在工业中的应用作了展望。     

钌催化的1,10-邻菲啰啉衍生物的不对称氢化反应

1,10-邻菲啰啉及其衍生物作为一类常见的双齿配体已广泛应用于金属催化的反应中,它们的直接不对称还原可以制备手性四氢-1,10-邻菲啰啉和八氢-1,10-邻菲啰啉两类具有潜在生理活性的杂环化合物,它们同时也可作为新型的含氮手性配体.但由于邻菲啰啉的强配位能力,可能导致金属催化剂中毒而失去活性,因此,过渡金属配合物催化1,10-邻菲啰啉的氢化反应还未见文献报道;而手性Br(?)nsted酸催化1,10-邻菲啰啉的不对称氢转移反应也仅有一例报道,且存在底物局限性及选择性较低等问题.中国科学院化学研究所范青华课题组利用手性二胺金属钌配合物     

手性离子液体研究进展

对近几年来手性离子液体的研究进展进行了全面综述,这些手性离子液体包括咪唑鎓盐、季铵盐、噁唑啉盐、噻唑啉盐、吡啶盐等;重点评述了手性离子液体的合成以及它们在有机化学中的应用,如作为反应溶剂和相转移催化剂、手性溶剂,手性助剂和手性位移试剂等。     

镁-双噁唑啉络合物催化3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应研究

报道了镁-双噁唑啉络合物体系催化的TMSCN与3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应.考察了BOX配体结构、配体与金属比例、温度、溶剂等对反应的影响.研究结果表明,使用双苄基取代的双噁唑啉配体与二丁基镁(物质的量比为2;1)在1,2-二氯乙烷中原位生成手性催化剂,催化剂用量为10 mol％,反应...     

金属催化硫醚的不对称氧化研究进展

手性金属络合物催化硫醚的不对称氧化是合成手性亚砜最有效的方法. 理性设计各种手性金属络合物催化剂应用于催化对映选择性氧化潜手性硫醚反应中, 近年来引起了化学家们较大的关注. 综述了各类手性金属络合物催化剂在硫醚不对称氧化中的应用.     

催化不对称傅-克反应研究进展

催化不对称傅-克反应是构建具有光学活性芳基化合物最有效的方法之一。自从1877年报道了首例傅-克反应后,该反应得到化学家们的关注。最近二十年,许多手性双功能有机小分子催化剂（如金鸡纳碱、手性脯氨醇硅醚、手性磷酸、手性硫脲等）以及金属与手性配体（如手性双氮氧、手性双唑啉、手性席夫碱）形成的配合物催化剂被应用到各类不对称傅-克反应中。本文主要从反应的芳基底物类型分类,对近年来酚、吡咯、呋喃以及噻吩参与的不对称傅-克反应进行简要概述,同时对这类反应所存在的问题和局限性进行总结,并对今后发展方向作了展望。     

修饰型多相手性催化剂在不对称合成中的应用

本文评述了修饰型多相手性催化剂在不对称合成中的应用。按照不同的制备方法及催化反应对一些多相催化体系进行了归类总结, 包括过渡金属手性配合物的固相化、修饰型手性固体催化剂、手性分子筛及嵌入型粘土手性催化剂。对酒石酸及金鸡纳碱修饰型金属催化剂的反应机理也进行了探讨。     

Stereogenic‐Only‐at‐Metal Asymmetric Catalysts

Chirality is an essential feature of asymmetric catalysts. This review summarizes asymmetric catalysts that derive their chirality exclusively from stereogenic metal centers. Reported chiral‐at‐metal catalysts can be divided into two classes, namely, inert metal complexes, in which the metal fulfills a purely structural role, so catalysis is mediated entirely through the ligand sphere, and reactive metal complexes. The latter are particularly appealing because structural simplicity (only achiral ligands) is combined with the prospect of particularly effective asymmetric induction (direct contact of the substrate with the chiral metal center). Challenges and solutions for the design of such reactive stereogenic‐only‐at‐metal asymmetric catalysts are discussed.     

Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 CpxMIII Catalysts

Transition-metal-catalyzed C−H functionalization reactions with Cp*M^III catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties in achieving catalytic stereocontrol using these catalysts due to their lack of additional coordination sites for external chiral ligands and the conformational flexibility of the Cp ligand, catalytic enantioselective C−H functionalization reactions using the Group 9 metal triad with Cp-type ligands have been intensively studied since 2012. In this minireview, the progress in these reactions according to the type of the chiral catalyst used are summarized and discussed. The development of chiral Cp^x ligands the metal complexes thereof, artificial metalloenzymes, chiral carboxylate-assisted enantioselective C−H activations, enantioselective alkylations assisted by chiral carboxylic acids or chiral sulfonates, and chiral transient directing groups are discussed.     

不对称反应的对映体过量值预测

建立了手性催化剂结构与反应产物对映体过量值的定量结构-活性相关性模型, 以辅助苯乙酮不对称氢转移反应的催化剂筛选. 手性催化剂由手性氨醇配体与金属络合物合成, 故采用构象独立手性指数或构象依赖手性指数描述手性氨醇配体, 采用指示变量区分金属络合物, 然后合并2个指数来描述手性催化剂. 通过遗传算法进行变量选择, 采用随机森林法建立数学模型以预测对映体过量值, 测试集的相关系数R²=0.769, 整个数据集的OOB(Out-of-bag)交叉验证结果为R²=0.785.     

Recent advances in asymmetric reactions catalyzed by chiral phosphoric acids

The very recent advances in chiral phosphoric acids (CPAs) catalyzed asymmetric reactions are discussed.     

Recent Advances in Asymmetric Catalysis Using p-Block Elements

The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone of organic synthesis. Typically, metal catalysts bearing chiral ligands as well as chiral organocatalysts have been employed for the enantioselective synthesis of organic compounds. In this review, we highlight the recent advances in main group catalysis for enantioselective reactions using the p-block elements (boron, aluminium, phosphorus, bismuth) as a complementary and sustainable approach to generate chiral molecules. Several of these catalysts benefit in terms of high abundance, low toxicity, high selectivity, and excellent reactivity. This minireview summarises the utilisation of chiral p-block element catalysts for asymmetric reactions to generate value-added compounds.     

Chiral monomeric organorhenium(VII) and organomolybdenum(VI) compounds as catalysts for chiral olefin epoxidation reactions

Several attempts have been made to transform the organometallic Re(VII) compound MTO and the (MoO₂)²⁺ moiety to chiral epoxidation catalysts by addition of chiral organic ligands. Being very efficient epoxidation catalysts in achiral reactions, it was hoped that these compounds could be transformed into chiral epoxidation catalysts by adding chiral Lewis base ligands. The major flaw of most of these attempts, however, was the weak coordination of the chiral Lewis base ligands to the metal center, which led either to high ees only at the very beginning of the catalytic reaction (low conversion) or to generally low enantiomeric excesses. The heterogenisation of the Mo(VI) complexes was, at least in some cases, successfully achieved but with the same drawbacks with respect to the ees as in the homogeneous phase. Currently, attempts are being made to synthesize organometallic Re(VII) and Mo(VI) complexes with stronger interactions between the metal containing moiety and the chiral ligand(s).     

Self-supported chiral catalysts for heterogeneous enantioselective reactions

The development of heterogeneous chiral catalysts for enantioselective reactions is highly desirable in order to overcome some drawbacks of homogeneous catalysts. Different from the conventional approaches by using various types of supports or biphasic systems for the recovery and reuse of homogeneous catalysts, a conceptually new strategy for heterogenization of homogeneous chiral catalysts, that is, a "self-supporting" approach, has been developed to use homochiral metal-organic coordination polymers generated by the self-assembly of chiral multitopic ligands with metal ions, and thus obviates the use of any support. In this concept article, the success of this "self-supporting" strategy will be exemplified in heterogeneous catalysis of asymmetric carbonyl-ene, sulfoxidation, epoxidation, and asymmetric hydrogenation reactions.     

稀土金属在不对称催化中的应用:从均相催化到异相催化

稀土金属的配位数较高,可通过容纳大型手性配体,构筑手性环境,催化不对称反应的定向发生,在工业生产特别是制药工程中具有重要应用价值.本文以Henry反应、Mannich反应和Strecker反应为例,总结回顾了稀土金属催化剂在此类反应中的设计思路、性能特点与应用前景,旨在展现稀土金属催化剂兼具融合均相催化与异相催化的优势...