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The inside cover picture shows the development of chiral pyridoxal and pyridoxamine catalysts by mimicking vitamin B6‐dependent enzymes. These chiral pyridoxals and pyridoxamines displayed extraordinary catalytic performances in asymmetric biomimetic transamination and Mannich reaction, to give various chiral α‐amino acids and α,β‐diamino acid esters in good yields with excellent diastero‐ and/or enantioselectivities. The research has provided some useful information for further applications of the catalytic power of vitamin B6 in the area of asymmetric cayalysis. More details are discussed in the article by Zhao et al. on page 103–112.
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Jiawei Lv Defang Ding Xuekang Yang Ke Hou Xiang Miao Dawei Wang Baichuan Kou Ling Huang Zhiyong Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7865-7869
Although it is well known that the amazing iridescent colors of the cuticle of beetles reflect the intricate nanoscale organization of bio‐fibers, artificial inorganic materials with comparable optical responses have not yet been synthesized from abiotic nanoscale building blocks. Such materials could find broad applications, including in circular polarizers, to generate circularly polarized luminescence, or in lasers. Herein, we describe a general method for the fabrication of biomimetic chiral photonic crystals by Langmuir–Schaefer assembly of colloidal inorganic nanowires. We not only reproduced the intricate helical structure and circularly polarized color reflection observed in beetles, but also achieved the highest chiroptical activity with a dissymmetry factor of ?1.6 ever reported for chiral inorganic nanostructures. More importantly, the programmable structural control based on the precise interlayer arrangement endows us with unprecedented freedom to manipulate the optical activity of as‐fabricated chiral photonic crystals. 相似文献
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Richard M. Kellogg 《Angewandte Chemie (International ed. in English)》1984,23(10):782-794
Ionophores, whether of natural or synthetic origin, encapsulate their ionic “guests” using noncovalent bonding. This encapsulation process resembles, at least superficially, the bonding of a substrate by an enzyme-active site. The analogy to enzymes can be extended further if the ionophore is provided with functional groups that can react with a suitable guest molecule bound in the cavity of the ionophore. We have embedded in the periphery of a macrocycle a 1,4-dihydropyridine, a mimic of the coenzyme NADH. The macrocycle, in addition to having (weak) ionophoric properties, is chiral. The strategy has led to compounds that react as artificial hydrogenases and which are capable of distinguishing, in a predictable fashion, between the prochiral faces of suitable carbonyl substrates. Ancillary developments from this approach have been many. A remarkably general method for the preparation of a wide variety of macrocycles has been developed which depends on some remarkable chemical idiosyncrasies of the cesium ion. In attempts to exploit the chemical possibilities of these macrocycles, unusual chemistry, possibly relevant to the action of the enzyme, 3-phosphoglyceraldehyde dehydrogenase, has been uncovered. In a similar vein, study of macrocycles has led to variants of the aldol condensation on chiral templates. Finally, catalytic CC bond formation mediated by transition metals is revealed to be an area in which chiral macrocycles can play a useful role by acting as chiral ligands for the transition metal. 相似文献
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自从 50年代早期发现 Ziegler- Natta催化剂以来 [1] ,立体有规聚合研究迅速发展 .80年代初 ,Kaminsky等 [2 ] 以手性配体锆化合物为催化剂 ,得到了高度等规的聚丙烯及聚 1 -丁烯 ,为 Ziegler-Natta催化剂均相化开拓了全新局面 .其后 Ziegler-Natta催化剂的一些链引发、链模板增长及终止机理 ,在均相条件下得以充分的研究 [3~ 5] .最近几年 ,又出现了用手性催化剂使无光学活性的单体聚合而成主链光学活性聚合物的研究 [6~ 8] ,并迅速成为金属有机化学家和高分子化学家关注的热点 .合成手性聚合物的研究 ,主要集中在模仿天然聚合物 ,阐… 相似文献
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J. K. Stille 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(13-14):1689-1693
By far the best method of synthesis of chiral organic compounds from prochiral substrates is through the use of chiral catalysts or enzymes. This approach has several advantages, the most important of which is that either the enzyme is naturally occurring or the catalyst can be easily generated from a naturally occurring chiral material. If resolution needs to be accomplished, it is carried out with small amounts of catalyst rather than with large quantities of product. Thus from a catalytic amount of chiral material large quantities of one enantiomeric product can be generated. 相似文献
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应用手性高分子试剂和催化剂的不对称有机合成反应 总被引:2,自引:0,他引:2
不对称有机合成是有机化学的前沿课题之一.本文综述了应用手性高分子试剂和催化剂对潜手性化合物通过不对称氧化、还原、烷基化、加成反应进行不对称合成的进展情况. 相似文献
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手性高烯丙基醇类化合物是一类非常重要的有机合成中间体,被广泛应用于药物分子和天然产物的合成中,不对称羰基ene反应是构建此类化合物最有效的方法之一,近年来已经取得了巨大进展。目前,在不对称羰基ene反应中的手性催化剂主要有如Mg、Ca、Sc、Ti、Co、Ni、Cu、Rh、Pd、Pt等金属与手性配体络合形成的配合物,以及一些手性有机小分子,大部分都取得了较好的催化活性与对映选择性。本文就此评述了各类手性催化剂在不对称羰基ene反应中的应用,不对称诱导反应的机理,以及催化剂分子结构及反应条件对催化活性和对映选择性的影响。 相似文献
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Hans H. Brintzinger David Fischer Rolf Mülhaupt Bernhard Rieger Robert M. Waymouth 《Angewandte Chemie (International ed. in English)》1995,34(11):1143-1170
Current studies on novel, metallocenebased catalysts for the polymerization of α-olefins have far-reaching implications for the development of new materials as well as for the understanding of basic reaction mechanisms responsible for the growth of a polymer chain at a catalyst center and the control of its stereoregularity. In contrast to heterogeneous Ziegler–Natta catalysts, polymerization by a homogeneous, metallocene-based catalyst occurs principally at a single type of metal center with a defined coordination environment. This makes it possible to correlate metallocene structures with polymer properties such as molecular weight, stereochemical microstructure, crystallization behavior, and mechanical properties. Homogeneous catalyst systems now afford efficient control of regio- and stereoregularities, molecular weights and molecular weight distributions, and comonomer incorporation. By providing a means for the homo- and copolymerization of cyclic olefins, the cyclopolymerization of dienes, and access even to functionalized polyolefins, these catalysts greatly expand the range and versatility of technically feasible types of polyolefin materials. For corrigendum see DOI: 10.1002/anie.199513681 相似文献
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Gaoyuan Ma Dr. Jun Deng Prof. Dr. Mukund P. Sibi 《Angewandte Chemie (International ed. in English)》2014,53(44):11818-11821
Can organocatalysts that incorporate fluxional groups provide enhanced selectivity in asymmetric transformations? To address this issue, we have designed chiral 4‐dimethylaminopyridine (DMAP) catalysts with fluxional chirality. These catalysts were found to be efficient in promoting the acylative kinetic resolution of secondary alcohols and axially chiral biaryl compounds with selectivity factors of up to 37 and 51, respectively. 相似文献
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自从L-脯胺酰胺被发现能高效催化不对称aldol反应以来,手性氨基酸酰胺催化剂的设计及不对称催化研究一直受到关注。特别是“烯胺-双氢键”模型的提出为设计新型有机小分子催化剂提供了理论依据,使催化剂的结构设计趋于多样化。本文重点总结了含有单氢键给体、双氢键给体及多氢键给体的氨基酸酰胺催化的不对称催化反应,主要包括不对称直接aldol反应、Mannich反应、Michael加成反应、环加成反应、串联环化反应、Biginelli反应等方面的研究进展。 相似文献
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《中国化学》2018,36(9):791-797
Transforming amino acids into novel catalysts and ligands is a remarkable subset of new catalyst development in order to imitate enzymatic efficiencies. Their ability to perform a variety of asymmetric catalytic reactions is complimented by their ready availability, rich transformations, stability and easy procedure. Herein, we focused on describing our endeavor of developing new catalysts and ligands from primary and secondary amino acids. It includes C2‐symmetric N,N'‐dioxides, guanidine‐amides, bispidine‐based diamines, and other organic salts. The account covered a brief introduction about their discovery, representative applications and related mechanisms. 相似文献
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近年来,用聚合物负载的手性催化剂和手性试剂完成的不对称合成反应主要集中在潜手性酮的不对称还原反应;烯烃的不对称双羟基化反应;烯烃的不对称环氧化反应;不对称Diels-Alder反应和饱和碳原子上的不对称取代反应。就近十年来聚合物负载手性催化剂和手性试剂的合成及应用进行了讨论。 相似文献
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Yuki Saito Shū Kobayashi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(1):e202313778
Transition metal-catalyzed enantioselective C−H bond functionalizations have become efficient methods for the synthesis of complex optically active molecules. Heterogeneous catalysts for this chemistry remain largely unexplored despite the advantages they offer in terms of ease of separation and reuse of catalysts. Herein, we report the development of heterogeneous chiral Rh catalysts for continuous-flow enantioselective hydroacylations. Heterogeneous catalysts could be prepared simply by mixing supports and Rh complexes. The prepared catalysts exhibited excellent activity and enantioselectivity affording optically active ketones in quantitative yields with 99 % ee's. Under the optimized reaction conditions, a turnover number >300 was achieved without the leaching of Rh species. The catalysts exhibited a wide substrate scope and in sequential-flow reactions with other heterogeneous catalysts, the syntheses of biologically active molecules and functional materials were demonstrated. 相似文献