手性salen(Mn)催化烯烃不对称环氧化反应的研究进展

烯烃的不对称环氧化物通过选择性开环或者官能团的转化,可以生成一系列有价值的手性化合物,被广泛用作医药、农药、香料等精细化学品的合成中间体.手性Mn(salen)金属配合物被证明是烯烃不对称环氧化最有效的催化剂之一.本文综述了近年来均相手性Mn(salen)催化剂、有机聚合物固载的手性Mn(salen)、无机载体固载手性...     

A new heterogeneous chiral (salen)manganese(III) system for enantioselective epoxidation of non‐functionalized olefins

This communication describes the design and application of a novel catalytic epoxidation system derived from the initial immobilization of a homogeneous sulfonato (salen)Mn(III) complex on two solid carriers (silica gel and siliceous earth) and subsequent dispersion of the supported manganese complexes into ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMImPF₆) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMImBF₄) for recycling. The performance of chiral (salen)Mn(III) system in enantioselective epoxidation of olefins was investigated systematically. Even higher enantioselectivity than that of the homogeneous counterpart was obtained with similar catalytic activity. In particular, the best catalytic result is that the combination of the silica gel‐supported (salen)Mn(III) catalyst and BMImPF₆ affords 97–100% ee for epoxidation of α‐methylstyrene, and high ee values were retained even after three cycles. Copyright © 2010 John Wiley & Sons, Ltd.     

磺甲基化ZPS-IPPA轴向固载手性Salen Mn(Ⅲ)催化剂及催化烯烃环氧化反应

以聚(苯乙烯-异丙烯膦酸)-磷酸氢锆(ZPS-IPPA)为载体,对其苯环氯甲基化、磺酸化后与手性Salen Mn(Ⅲ)轴向配位,合成了一类新的固载型手性Salen Mn(Ⅲ)催化剂,采用FTIR,XPS,SEM,TEM,N2吸附等对催化剂表征.分别在次氯酸钠溶液和间氯过氧苯甲酸氧化体系中,考察了固载催化剂对苯乙烯、α-甲基苯乙烯、茚等非功能化烯烃不对称环氧化反应的催化性能,结果表明,与均相催化剂相比,对映体选择性明显提高.尤其在m-CPBA/NMO氧化体系中0℃反应12h,茚的环氧化物的转化率及ee值均达到99%以上.并且催化剂容易分离,回收使用5次仍能保持较好的催化性能.     

Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

This article details the enantioselective catalytic performance of crosslinked, polymer immobilized, Ir‐based, chiral complexes for transfer hydrogenation of cyclic imines to chiral amines. Polymerization of the achiral vinyl monomer, divinylbenzene, and a polymerizable chiral 1,2‐diamine monosulfonamide ligand followed by complexation with [IrCl₂Cp*]₂ affords the crosslinked polymeric chiral complex, which can be successfully applied to asymmetric transfer hydrogenation of cyclic imines. Polymeric catalysts prepared from amphiphilic achiral monomers have high catalytic activity in the reaction and can be used both in organic solvents and water to give chiral cyclic amines with a high level of enantioselectivity (up to 98% ee). The asymmetric reaction allows for reuse of the heterogeneous catalyst without any loss in activity or enantioselectivity over several runs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3037–3044     

手性过渡金属(Mn, Co, Ni)-Salen配合物催化NaOCl不对称环氧化苯乙烯的反应研究

本文论述了由手性1, 2-二苯基乙二胺与适当取代的邻羟基苯甲醛生成的希佛碱作为过渡金属Co(II)、Ni(II)、Mn(II)的配体合成的6种过渡金属-Salen配合物在NaOCl下均相催化苯乙烯不对称环氧化反应的效果。对环氧化反应进行控制性研究, 我们发现环氧化反应与中心金属离子的相关性可能主要源于配体结构、金属离子的选择及二者结合形成的配合物的空间构型。好的不对称环氧化反应催化剂要求中心金属离子具有适当的氧化还原电位, 对底物烯烃因其取代基的大小, 催化剂结构的空间构型应有好坏之分, 我们得到的循环伏安数据及实验结果部分说明这一点。同时对手性镍(II)-Salen及手性锰(III)-Salen配合物的催化反应机理配合实验现象分别作出假设, 都经过自由基历程, 但却是截然不同的活性氧化物种, 同时, 由于起主要作用的不对称诱导因素不同, 不对称诱导方向有异。对同一催化剂在不同pH值下起作用的活性氧化物种类别也可能不同。     

An effective approach for the immobilization of chiral Mn(III) salen complexes through a supported ionic liquid phase

An effective method based on supported ionic liquid system was employed to immobilize chiral Mn(III) salen complexes. The prepared heterogeneous catalysts exhibited excellent activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Especially, in the epoxidation of α-methylstyrene, both the conversion and ee value could exceed 99%. Furthermore, the immobilized catalysts were stable and could be recycled three times without loss of activities.     

新型晶态层状载体聚(苯乙烯-苯乙烯基膦酸)-磷酸锌轴向固载手性Salen Mn(Ⅲ)的合成及催化烯烃的环氧化性能

在温和条件合成了新型晶态层状有机聚合物-无机杂化载体材料聚(苯乙烯-苯乙烯基膦酸)-磷酸锌, 结合实验数据提出了其可能的理想结构模型. 对该载体进行氯甲基化和酚羟基化修饰后, 轴向配位固载手性Salen Mn(Ⅲ), 合成了一类新型的多相催化剂. 以间氯过氧苯甲酸为氧源, 考察了其对α-甲基苯乙烯及茚不对称环氧化反应的催化性能. 结果表明, 这类固载催化剂具有与均相Jacobsen催化剂相当或更高的催化活性和对映选择性, 并具有优良的重复使用性. 特别是在该氧化体系中, 当无助催化剂N-甲基吗啉氮氧化物(NMO)参与时, 固载催化剂获得更高的转化率及e.e.值, 这为其扩大化生产增加了可能性.     

手性联萘酚配合物催化的缺电子烯烃不对称环氧化反应

缺电子烯烃的不对称环氧化反应是有机合成领域最具有挑战性的课题之一。手性联萘酚配体所修饰的催化剂是一种很优异的C2轴对称手性诱导源,可以催化各种α,β－不饱和羰基化合物如α,β－不饱和酮、α,β－不饱和羧酸脂等的不对称环氧化反应,具有良好的催化活性和对映选择性。本文对由手性联萘酚类配体所修饰的小分子催化剂、聚合物负载的催化剂和自负载催化剂在不饱和羰基化合物的催化不对称环氧化反应中的应用进行了综述,探讨了催化剂结构、配位金属原子、添加物、氧化剂、溶剂和反应温度等因素对手性联萘酚催化剂催化效能和对映选择性的影响。     

Synthesis of catalytically active polymer-bound Schiff base manganese complexes for selective epoxidation of unfunctionalized olefins

A polymerizable unsymmetric tetradentate Schiff base with one vinyl group 3 was synthesized and copolymerized with styrene in toluene. Mn(III) ion was quantitatively incorporated into the copolymers by the functional moieties. The resulting linear polymer-bound manganese complexes ( 4a ′ and 4b ′) were used as catalyst under homogeneous condition for selective epoxidation of unfunctionalized olefins (i.e. styrene, α-methylstyrene and cyclohexene) at room temperature in the presence of iodosylbenzene (PhIO) as the terminal oxidant. The efficacy of epoxidation using the polymeric catalysts was comparable to that of the monomolecular analog. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3249–3254, 1997     

Chiral Mn(III) salen complex immobilized on imidazole-modified mesoporous material via co-condensation method as an effective catalyst for olefin epoxidation

An imidazole modified mesoporous material has been prepared through a co-condensation procedure and adopted to covalently anchor chiral Mn(III) salen complex. The active centers in the as-synthesized catalyst were presented in the form of ionic species. The results of XRD, FTIR, DRUV-Vis, and N₂ sorption confirmed the successful immobilization of chiral Mn(III) salen complex inside the channels of the modified support and the maintenance of the mesoporous structure of parent support in the immobilized catalyst. This heterogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to those of the homogeneous counterpart in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, notably high turnover frequencies have been obtained over this heterogeneous catalyst for the relatively short reaction time and low catalyst amount, due in part to the ionic property as well as the uniform distribution of the active centers.     

手性过渡金属(Mn,Co,Ni)-Salen配合物催化NaOCl不对称环氧化苯乙烯的反应研究

本文论述了由手性1,2-二苯基乙二胺与适当取代的邻羟基苯甲醛生成的希佛碱作为过渡金属Co(Ⅱ)、Ni(Ⅲ)、Mn(Ⅲ)的配体合成的6种过渡金属-Salen配合物在NaOCl下均相催化苯乙烯不对称环氧化反应的效果。对环氧化反应进行控制性研究,我们发现环氧化反应与中心金属离子的相关性可能主要源于配体结构、金属离子的选择及二者结合而形成的配合物的空间构型。好的不对称环氧化反应催化剂要求中心金属离子具有适当的氧化还原电位,对底物烯烃因其取代基的大小,催化剂结构的空间构型应有好坏之分,我们得到的循环伏安数据及实验结果部分说明这一点。同时对手性镍(Ⅱ)-Salen及手性锰(Ⅲ)-Salen配合物的催化反应机理配合实验现象分别作出假设,都经过自由基历程,但却是截然不同的活性氧化物种,同时,由于起主要作用的不对称诱导因素不同,不对称诱导方向有异。对同一催化剂在不同pH值下起作用的活性氧化物种类别也可能不同。     

A novel layered organic polymer-inorganic hybrid zinc poly (styrene-phenylvinylphosphonate)-phosphate immobilized chiral salen Mn(III) catalyst large-scale asymmetric epoxidation of unfunctionalized olefins

A novel layered organic polymer-inorganic hybrid zinc poly (styrene-phenylvinylphosphonate)-phosphate (ZnPS-PVPA) has been synthesized under mild conditions and diphenol-modified ZnPS-PVPA was used to successfully immobilize the chiral salen Mn(III) by axial coordination. The obtained heterogeneous chiral catalysts exhibited excellent activities and enantioselectivities using sodium periodate as an oxidant for asymmetric epoxidation of unfunctionalized olefins, especially for the epoxidation of α-methylstyrene (conversion: up to 97%; ee: exceed 99%). Moreover, these synthesized catalysts were relatively stable and could be expediently separated from the reaction system, and could be recycled at least ten times without obvious loss of activity and enantioselectivity. These novel catalysts could be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which offer a great possibility for application in industry.     

三苯甲基取代烯烃的环氧化研究

合成了6种三苯甲基取代烯烃. 以二甲基二氧杂环丙烷作为主要氧化剂, 在催化剂(R,R)-Salen Mn(III)的催化下, 进行不对称环氧化, 其不对称环氧化产物ee值较高(81%). 初步研究表明, 二甲基二氧杂环丙烷(DMD)和(R,R)-Salen Mn(III)的环氧化体系对于含亚甲基的三苯甲基取代的烯烃的氧化产率高但对映选择性差, 对于不含亚甲基的三苯甲基取代的烯烃的氧化产率低但对映选择性好.     

Polymer-supported salen complexes for heterogeneous asymmetric synthesis: Stability and selectivity

This paper details the enantioselective performance of styrene/divinylbenzene-supported Mn- and Cr-based salen complexes for the epoxidation of olefins and the ring-opening of epoxides to azido-silyl ethers. The Mn catalyst produced the epoxides of 1,2-dihydronaphthalene, styrene, and cis-β-methylstyrene with enantiomeric excesses (ee's) of 46, 9, and 79%, respectively. For the Cr catalyst, the enantioselective ring-opening of epoxyhexane, propylene oxide, and cyclohexene oxide with trimethylsilyl azide proceeded with ee's of 34, 36, and 6%, respectively. Upon recycle of these heterogeneous catalysts, a degradation process was noted for the Mn-catalyst under the conditions for epoxidation that resulted in oxidation and decomposition of the ligand. This process also affects the homogeneous catalyst, thereby limiting the recyclability of both the homogeneous Mn catalyst and its heterogenized version for this reaction. The Cr-catalyzed reaction to ring-open epoxides employs milder conditions and allowed reuse of the heterogeneous catalyst without loss of activity or enantioselectivity through three runs with epoxyhexane. During reaction, the leaching of Cr from the heterogeneous catalyst is less than 0.1%, suggesting possible reuse of the catalyst over hundreds of cycles before reloading the polymer-supported salen ligand with metal would be necessary. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3888–3898, 1999     

Axially coordinated chiral salen Mn(iii) anchored onto azole onium modified ZnPS-PVPA as effective catalysts for asymmetric epoxidation of unfunctionalized olefins

A series of chiral salen Mn(iii) immobilized onto azole onium modified zinc poly(styrene-phenylvinyl phosphonate)-phosphate (ZnPS-PVPA) were prepared. The catalysts were characterized by FT-IR, diffusion reflection UV-vis, AAS, N(2) volumetric adsorption, SEM, TEM, XPS, XRD, TG and elemental analysis. The results showed that the chiral salen Mn(iii) complex was successfully immobilized onto ZnPS-PVPA. These prepared catalysts were evaluated in the asymmetric epoxidation of unfunctionalized olefins with m-CPBA and NaIO(4) as oxidants and demonstrated higher catalytic activities than those of the corresponding homogeneous chiral salen Mn(iii) catalyst under the same conditions. Moreover, these heterogeneous catalysts were stable and could be recycled nine times without significant loss of activity. Furthermore, this novel type of catalyst could also be validly used in large-scale reactions with superior catalytic disposition being maintained at the same level, which indicated the potential for applications in industry.     

多孔有机含BINAP聚合物负载Rh催化剂在苯乙烯不对称氢甲酰化中的应用:柔性手性口袋对产物对映体选择性的提高作用

不对称氢甲酰化是合成具有单一光学活性物质(如光学活性的醛、α-氨基酸和醇等)最为重要的反应之一.尽管不对称氢甲酰化反应的研究超过40年,但仍然是催化体系中具有挑战性的课题.该反应涉及到产物的化学选择性、立体选择性和对映体选择性的优化.目前,在Rh催化体系中,使用磷-亚磷酸酯手性配体或双亚磷酸酯配体可以在不对称氢甲酰化反应中取得优异的催化性能.然而在Rh/手性双膦配体催化体系中,不对称氢甲酰化反应性能通常很低.以BINAP配体为例,负载Rh金属后,在催化苯乙烯不对称氢甲酰化反应中,产物的ee值只有25％.同时,由于均相催化体系存在催化剂回收和产物提纯等问题,因此有必要研究多相不对称氢甲酰化反应催化剂.本文使用乙烯基修饰的BINAP配体5,5'-divinyl-BINAP与具有不同结构的共聚单体二乙烯基苯或1,3,5-三乙烯基苯基苯共聚,得到具有不同孔结构的聚合物Poly-1和Poly-2.为了比较,利用线性共聚单体乙二醇二甲基丙烯酸甲酯与乙烯基BINAP共聚得到聚合物Poly-3.上述三种聚合物材料负载金属Rh后,用作苯乙烯不对称氢甲酰化反应的催化剂.固体13C核磁分析表明,三种聚合物材料负载金属后仍然保持较为稳定的C骨架结构.通过31p核磁可以看到,嵌入在材料骨架中的BIANP仍然保持未被氧化的状态.N2物理吸附结果发现Poly-1和Poly-2具有较大的比表面积和孔体积,而Poly-3的比表面积最小.热重分析显示,这些材料具有较高的热稳定性.在不同反应溶剂中催化剂活性差异较大.通过优化反应温度和合成气压力后,催化剂Rh/Poly-1在80℃和0.2 MPa下产物的对映体选择性可高达58.9％,支链醛与直链醛的比值为8.5;而在相同反应条件下,均相催化剂Rh-BINAP的ee值仅为35.3％,但高于Rh/Poly-3.这是由于三个多相催化剂骨架中BINAP周围环境不同所致.前两个催化剂中,BINAP与空间位阻较大的单体相连接,使得反应底物按照特定方向与催化活性位点接触,形成了类似于手性口袋的结构.而Rh/Poly-3中,BIANP周围是线性的共聚单体,不能形成有效的手性口袋结构.Rh/Poly-1重复使用7次后,催化活性没有显著下降.拓展X射线吸收精细结构表征结果表明,Rh/Poly-1催化剂使用前没有Rh-Rh键存在,但经重复使用后,Rh金属部分聚集,生成了Rh-Rh键.球差电镜照片也证实了这一点.     

Synthesis of new binol based [1+1] macrocyclic chiral manganese(III) Schiff bases as catalysts for asymmetric epoxidation

A series of new chiral binol based [1+1] macrocyclic Schiff bases have been synthesized in high yields in short reaction times via cyclo-condensation of dialdehydes with long tethers and chiral diamines. Macrocyclic Mn(salen) complexes containing N₂O₂ salen units incorporated with spacers of increased tether lengths were synthesized and characterized. The newly synthesized catalyst system was successfully employed for the enantioselective epoxidation of unfunctionalized olefins with high yields and good enantioselectivity.     

Heterogeneous chiral Mn(III) salen catalysts for the epoxidation of unfunctionalized olefins immobilized on mesoporous materials with different pore sizes

Two chiral Mn(III) salen complexes were immobilized onto a series of mesoporous MCM-41 and MCM-48 materials with different pore sizes and the as-synthesized catalysts were active and enantioselective for the asymmetric epoxidation of styrene and indene. The results of XRD, FTIR, DR UV-vis, and N₂ sorption showed that the chiral Mn(III) salen complexes were anchored in the channels of mesoporous materials. The influence of organic silicane dosage on the catalytic performance was studied and the optimum dosage of organic silicane for preparing heterogeneous catalysts was determined. Furthermore, the effect of the fine-tuning of pore size on the performance of heterogeneous catalysts was discussed. In general, larger pore size of the supports could lead to higher conversions and the compatible pore size with substrate may be responsible for the improved enantiomeric excess (ee) values.     

Design and development of highly effective Lewis acid catalysts for enantioselective Diels-Alder reactions

This report describes the design and development of chiral Co(III)-salen catalysts for enantioselective Diels-Alder reactions. A crystal structure of a Co-salen catalyst with two equivalents of benzaldehyde provided insight on the factors that may be important for enantioselectivity. On the basis of this structural information, new catalysts were prepared in which the "bay region" tert-butyl groups were replaced by trimethylsilyl groups. The new silyl-substituted catalysts were exceptionally effective (catalyst loadings down to 0.05 mol %) and convenient to use-room temperature, under an air atmosphere, using a minimum amount of solvent.     

Asymmetric heterogeneous carbene transfer catalyzed by optically active ruthenium spirobifluorenylporphyrin polymers

Anodic oxidation of chiral ruthenium complexes of spirobifluorenylporphyrins leads to the coating of the working electrode by insoluble optically active films whose electrochemical behaviour and physicochemical properties are described. After removal from the electrode, the ruthenium-complexed polymers were evaluated as enantioselective catalysts for the cyclopropanation of olefins by ethyl diazoacetate. The results show the reactions proceeded very efficiently at room temperature with excellent yields (80–90%) and moderate enantioselectivities (up to 53% at −40 °C). The chiral electrosynthesized polymer catalysts can be recycled by simple filtration and reused even up to the seventh cycle with only a slight decrease of activity and enantioselectivity.