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1.
Catalysis with lanthanide (Ln) complexes has been underestimated for long time, although Ln(III) complexes have great advantages as Lewis acid catalysts for "asymmetric" carbon-carbon bond-forming reactions. Lanthanide complexes are highly active in ligand-substitution reactions, especially with hard ligands. The association with substrates and dissociation of products are achieved fast enough for high catalyst efficiency. The asymmetric catalysis of organic reactions can be greatly advanced by the use of Ln complexes with chiral ligands such as binaphthol (binol). Ln(II) complexes are good reducing agents, which can be used in a wide variety of synthetically important reactions; when chiral ligands are used, many of these reactions are highly stereoselective. In the context of "green chemistry", the development of asymmetric Ln catalysts, and their recyclable use, is of increasing importance. This review gives an overview of the most recent developments in catalysis with lanthanide(II) and lanthanide(III) complexes.  相似文献   

2.
An efficient asymmetric catalyst relies on the successful combination of a large number of interrelated variables, including rational design, intuition, persistence, and good fortune-not all of which are necessarily well-understood; this renders such practice largely empirical. As a result, the possibility of using combinatorial chemistry methods in asymmetric catalysis research has been widely recognized to be highly desirable. In this account, we attempt to show the principle and application of combinatorial approach in the discovery of chiral catalysts for enantioselective reactions. The concept focuses on the strategy for the creation of a modular chiral catalyst library by two-component ligand modification of metal ions on the basis of molecular recognition and assembly. The self-assembled chiral catalyst with two different ligands indeed exhibited synergistic effects in terms of both enantioselectivity and activity in comparison with its corresponding homocombinations in many reactions. The examples described in this paper demonstrated the powerfulness of combinatorial approach for the discovery of novel chiral catalyst systems, particularly for the development of highly efficient, enantioselective, and practical catalysts for enantioselective reactions. We hope this concept will stimulate further work on the discovery of more highly efficient and enantioselective catalysts, as well as unexpected classes of catalysts or catalytic enantioselective reactions in the future with the help of a combinatorial chemistry approach.  相似文献   

3.
石磊  王正  王兴旺  李明星  丁奎岭 《有机化学》2006,26(10):1444-1456
较系统地介绍了手性催化剂负载的一种新方法(即“自负载”策略)及其在非均相不对称催化反应中应用的最新进展. 与传统的负载模式不同, “自负载”策略中利用含双或多官能团的配体与金属通过自组装形成的有机-无机聚合物做为催化剂, 因此不需使用任何载体. “自负载”手性催化剂在若干非均相不对称催化反应中显示了优秀的催化活性和对映选择性并且能够简单回收再利用, 为手性催化剂的负载化提供了一个新的策略.  相似文献   

4.
三氟甲基磺酸铜 [Cu(OTf) 2 ]与各种手性磷氮配体络合催化不对称合成已取得了巨大进展 .详细评述了近五年来该类手性铜催化剂在各种不对称催化反应中的最新应用  相似文献   

5.
Catalytic reactions of diazoacetates tethered through zero, one, two, and three ethylene glycol units to an allyl group have been investigated for chemoselectivity, diastereoselectivity, and enantioselectivity. Results from cyclopropanation, carbon-hydrogen insertion, and oxonium ylide generation are compared from reactions of achiral and chiral catalysts of copper(I) and dirhodium(II) carboxylates and carboxamidates. Relative to results from intermolecular reactions of ethyl diazoacetate with allyl ethyl ether, intermolecular reactions show a diversity of selectivities including preference for the opposite configurational arrangement from the one preferred in corresponding intermolecular cyclopropanation reactions. Enantioselectivities for cyclopropanation are dependent on the catalyst ligands in a manner that reflects divergent trajectories of the carbon-carbon double bond to the reacting carbene center. Enantioselectivity increases as a function of ring size with chiral copper catalysts, but the reverse occurs with chiral dirhodium(II) carboxamidates. Mechanistic implications, including those related to the conformation of the reacting metal carbene, offer a new dimension to understanding of enantioselectivity in catalytic asymmetric cyclopropanation reactions.  相似文献   

6.
汪海明  王正  丁奎岭 《化学进展》2010,22(7):1471-1481
催化剂的负载和回收再利用是提高其使用效率、降低反应成本和减少金属离子对产物污染的一条有效途径。与传统的负载模式不同, 手性自负载催化剂通过含双或多官能团的手性配体与金属通过自组装形成一类有机-无机聚合物,因此无需使用任何载体,即能够有效地实现手性催化剂的回收和再利用。近年来,手性自负载催化剂作为一种新的负载模式,已经成功地应用于一些非均相催化的不对称反应中。本文概述了手性自负载催化剂的在一些不对称催化反应研究中取得的新进展。  相似文献   

7.
Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals  相似文献   

8.
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.  相似文献   

9.
The start of the development of catalysts for asymmetric hydrogenation was the concept of replacing the triphenylphosphane ligand of the Wilkinson catalyst with a chiral ligand. With the new catalysts, it should be possible to hydrogenate prochiral olefins. Knowles and his co‐workers were convinced that the phosphorus atom played a central role in this selectivity, as only chiral phosphorus ligands such as (R,R)‐DIPAMP, whose stereogenic center lies directly on the phosphorus atom, lead to high enantiomeric excesses when used as catalysts in asymmetric hydrogenation reactions. This hypothesis was disproven by the development of ligands with chiral carbon backbones. Although the exact mechanism of action of the phosphane ligands is not incontrovertibly determined to this day, they provide a simple entry to a large number of chiral compounds.  相似文献   

10.
D-葡萄糖手性衍生物, 在不对称催化反应中的研究进展十分迅速, 综述了近年来D-葡萄糖手性衍生物直接作为催化剂催化不对称相转移Michael加成反应、氢硅烷化自由基链反应等和作为催化剂配体在不对称环氧化、氰硅烷化及Reformatsky等反应中的应用进展.  相似文献   

11.
金属催化的不对称氢化反应研究进展与展望   总被引:1,自引:0,他引:1  
谢建华  周其林 《化学学报》2012,70(13):1427-1438
手性过渡金属络合物催化的不对称氢化反应是合成光学活性化合物的重要方法. 本文从手性配体及手性催化剂、不对称催化新反应、新方法和新策略三个方面简要评述新世纪以来过渡金属催化的不对称氢化反应研究领域的新进展. 从新世纪初至今, 手性单磷配体得到了复兴, 出现了如MonoPhos、SiPhos、DpenPhos等高效单齿亚磷酰胺酯配体; 磷原子手性(P-手性)配体也得到了快速发展, 如BenzP*、ZhanPhos、TriFer等已成为新的高效手性双膦配体; 螺环骨架手性配体成为新世纪手性配体设计合成的亮点, 除了SiPhos、SIPHOX、SpinPHOX等高效手性螺环配体外, 手性螺环吡啶胺基磷配体SpiroPAP的铱催化剂成为目前最高效的分子催化剂. 不对称催化氢化新反应研究也取得了突破, 如非保护烯胺、杂芳环化合物及N-H亚胺的氢化等反应都实现了高对映选择性. 自组装手性催化剂、树枝状手性催化剂、铁磁性纳米负载的可回收手性催化剂, 以及“混合”配体手性催化剂等新方法和新策略也在不对称催化氢化反应中得到了应用. 然而, 手性过渡金属络合物催化的不对称氢化研究仍然充满挑战, 也期待新的突破.  相似文献   

12.
A new type of dendritic 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN)-derived Schiff-base ligands have been synthesized and applied to the titanium-catalyzed hetero-Diels-Alder reaction of Danishefsky's diene with aldehydes. These reactions afforded the corresponding 2-substituted 2,3-dihydro-4H-pyran-4-ones in quantitative yields and with excellent enantioselectivities (up to 97.2 % ee). The disposition of the dendritic wedges and the dendron size in the ligands were found to have significant impact on the enantioselectivity of the reaction. The recovered dendritic catalyst could be reused without further addition of the Ti source or a carboxylic acid additive for at least three cycles, retaining similar activity and enantioselectivity. The high stability of this type of assembled dendritic titanium catalyst may be attributed to the stabilization effect of large-sized dendron units in the catalyst molecule. The other important phenomenon observed with this catalyst system is that a higher degree of asymmetric amplification has been achieved by attachment of the dendron unit to the chiral ligand, which represents a new advantage of dendrimer catalysts for asymmetric reactions using chiral ligands of lower optical purity.  相似文献   

13.
Homogeneous asymmetric catalysis is one of the most important developments in chemistry in the past several decades. Attachment of chiral ligands to a polymeric support offers important advantages such as facilitated workup procedures, easy recovery and reuse of the catalyst in catalytic reactions. Various chiral ligands supported on polymer have been used as catalysts.  相似文献   

14.
While nonracemic catalysts can generate nonracemic products with or without the nonlinear relationship in enantiomeric excesses between catalysts and products, racemic catalysts inherently give only a racemic mixture of chiral products. Asymmetric catalysts, either in nonracemic or racemic form, can be further evolved into highly activated catalysts with association of chiral activators. This asymmetric activation process is particularly useful in racemic catalysis through selective activation of one enantiomer of the racemic catalyst. Recently, a strategy whereby a racemic catalyst is selectively deactivated by a chiral additive has been reported to yield nonracemic products. However, reported herein is an alternative and conceptually opposite strategy in which a chiral activator selectively activates, rather than deactivates, one enantiomer of a racemic chiral catalyst. The advantage of this activation strategy over the deactivation counterpart is that the activated catalyst can produce a greater enantiomeric excess in the products-even with the use of a catalytic amount of activator relative to chiral catalyst-than that attained by the enantiomerically pure catalyst on its own. Therefore, asymmetric activation could provide a general and powerful strategy for not only the use of atropisomeric, racemic ligands but also chirally flexible and proatropisomeric ligands without enantiomeric resolution!  相似文献   

15.
《Tetrahedron: Asymmetry》2014,25(3):278-283
A series of chiral N,N′-dialkyl-1,2-cyclohexanediamine derivatives were designed, synthesized, and applied as ligands in asymmetric copper(II)-catalyzed Henry reactions. The catalysts based on such ligands and copper(II) acetate were found to promote asymmetric Henry reactions between aromatic/aliphatic aldehydes and nitromethane efficiently, and could provide the corresponding β-nitroalcohols in very good yields and with enantioselectivities of up to 93.6%.  相似文献   

16.
催化不对称反应最新进展(Ⅱ)-组合化学方法之 应用   总被引:3,自引:0,他引:3  
丁奎岭 《有机化学》2000,20(5):613-622
组合化学技术已经成为药物、新型固体材料和催化剂合成、评价和筛选的一种有力工具,最近它在催化不对称反应的手性催化剂高效率合成与筛选方面的应用也受到了重视,本文将综述组合化学技术在发展不对称合成新型催化剂方面的应用。第一部分主要介绍手性催化剂(或配体)库的固相平行合成;第二部分重点总结了所建立的手性催化剂库的高效率评价技术及其应用。  相似文献   

17.
Catalytic asymmetric aldol reactions of silyl enol ethers with aldehydes (Mukaiyama aldol reactions) have been performed using novel chiral zirconium catalysts. The reactions proceeded in high yields under mild conditions, and anti-adducts were obtained in high diastereo- and enantioselectivities. The catalysts were first prepared from zirconium(IV) tert-butoxide (Zr(O(t)Bu)(4)), (R)-3,3'-diiodo-1,1'-binaphthalene-2,2'-diol ((R)-3,3'-I(2)BINOL), a primary alcohol, and a small amount of water. It was revealed that the primary alcohol played an important role in completing the catalytic cycle and that a small amount of water was essential for obtaining high selectivities. Moreover, activities of the chiral zirconium catalysts were enhanced by using new ligands, (R)-3,3'-I(2)-6,6'-X(2)BINOL (X = Br, I, C(2)F(5)), and it has been shown that even aldol reactions of less reactive substrates proceeded smoothly using the novel zirconium catalysts. Finally, NMR studies of these catalysts were performed, which suggested that the catalyst would form a dimeric structure and that the water affected the catalyst formation.  相似文献   

18.
A new series of Schiff bases derived from Cinchona alkaloids were developed as chiral ligands for the copper(II)-catalyzed asymmetric Henry reaction. The optimized catalyst can promote the Henry reaction of both aromatic and aliphatic aldehydes with nitromethane or nitroethane. Those reactions can afford the chiral β-nitro alcohol adducts with high enantioselectivities.  相似文献   

19.
The cycloaddition of a chiral ligand containing a terminal alkyne to a soluble polymer containing an azide provides a convenient means for the attachment of an asymmetric transfer hydrogenation catalyst to a soluble polymer support. Using these ligands in complexes with Ru(II), gave good results in terms of conversion and enantioselectivity (up to 95% ee) in ketone reduction reactions.  相似文献   

20.
New chiral sulfoxide-1,3-oxazoline ligands have been developed as chiral ligands for Lewis acid-catalyzed asymmetric Diels-Alder reactions. The use of chiral sulfinyl 1,3-oxazoline ligands in copper(II)-catalyzed asymmetric Diels-Alder reactions provided an endo cycloadduct as a major product with moderate enantioselectivity. A rationale is proposed for the mechanism of the asymmetric induction.  相似文献   

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