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1 Chinese Journal of Catalysis 35 (2014) 催化学报 2014 年第 35 卷第 9 期 available at journal homepage: Article Chiral Mn III (Salen) supported on tunable phenoxyl group modified zirconium poly (styrene phenylvinylphosphonate) phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins Xiaochuan Zou a,b, *, Kaiyun Shi a, Cun Wang a a Department of Biological and Chemical Engineering, Chongqing University of Education, Chongqing , China b College of Chemistry and Chemical Engineering, Research Institute of Applied Chemistry, The Key Laboratory of Applied Chemistry of Chongqing Municipality, The Key Laboratory of Eco environments in Three Gorges Reservoir Region Ministry of Education, Southwest University, Chongqing , China A R T I C L E I N F A B S T R A C T Article history: Received 30 January 2014 Accepted 21 February 2014 Published 20 September 2014 Keywords: Zirconium Poly(styrene phenylvinylphosphonate) phosphate Chiral Jacobsen s Catalyst Tunable phenoxyl linker groups Asymmetric Epoxidation of Alkenes We have developed a series of chiral Mn III (Salen) (chiral Jacobsen s catalyst) catalysts that were axially supported onto zirconium poly(styrene phenylvinylphosphonate) phosphate through tunable phenoxyl linkers of varying steric hindrance, and evaluated their performance as catalysts (Cat1 Cat3) for the epoxidation of unfunctionalized olefins using m chloroperbenzoic acid as an oxidant. The corresponding non supported analogues (Cat4 Cat6) were also prepared and tested under similar conditions. The results demonstrated that the incorporation of substituents at the ortho positions of the tunable phenoxyl linkers had a critical effect on the catalytic activity. Furthermore, the enantioselectivity increased as the steric hindrance imposed by the linker increased, although this also led to a decrease in the conversions under the same reaction conditions, especially for heterogeneous epoxidation. The heterogeneous system also displayed high ee values and conversions in the absence of the axial additive N methylmorpholine N oxide, which is commonly required to improve the catalytic activity of epoxidation reactions, especially for the epoxidation of α methylstyrene. The reusability of the catalyst was also evaluated over 11 catalytic cycles, with no significant reduction observed in the catalytic activity or enantioselectivity after five runs. 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved. 1. Introduction Epoxides are an important structural class of industrial chemicals that are regularly used as intermediates in organic synthesis, and the catalytic epoxidation of alkenes represents a useful method for the formation of epoxides [1]. Among the various catalysts available for the epoxidation of alkenes, chiral Mn III (Salen) is one of the most practical and efficient in terms of the yields and ee values of the resulting epoxides [2]. Environmental concerns associated with the separation and recycling of the catalysts used in organic synthesis, as well as the purification of products resulting from catalytic processes, have led * Corresponding author. Tel: ; Fax: ; E mail: zxcvip2003@163.com This work was supported by the Basic and Frontier Research Project of Chongqing (cstc2013jcyja50013), Scientific and Technological Research Program of Chongqing Municipal Education Commission (KJ131504), and the Innovation Team Building at Institutions of Higher Education in Chongqing (KJTD201325). DI: /S (14) Chin. J. Catal., Vol. 35, No. 9, September 2014

2 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) to the deployment of considerable research efforts towards the development of solid supported Mn III (Salen) catalysts [3 6]. Several supports have been developed for Salen catalysts, including high molecular weight polymer and inorganic supports, as well as supports based on dendrimers and oligomers [7 12]. Although significant advances have been made in recent years towards the development and application of recoverable catalysts, reports pertaining to the effect of inorganic organic hybrid supports and linker group to the activity of the catalyst have been scarce. During the course of the last two decades, research within our group has been primarily directed towards the development and application of novel organic inorganic hybrid materials [13 19]. Extremely high levels of catalytic activity were recently observed in the epoxidation of unfunctionalized olefins using a Mn III (Salen) catalyst immobilized onto a range of inorganic organic hybrid materials, including zirconium oligo polstyrenylphosphonate phosphate (ZSPP) [13 15], zirconium poly(styrene isopropenyl phosphonate) phosphate (ZPS IPPA) [16,17], and ZPS PVPA [18,19]. Furthermore, the use of chiral Mn III (Salen) axially immobilized onto amorphous phenoxyl modified ZPS PVPA as a catalyst resulted in a remarkable increase in the conversion and ee values for the asymmetric epoxidation of olefins when the reaction was conducted in the absence of expensive coordinating axial additive, which is contrary to the results previously published in the literature pertaining to both homogeneous and heterogeneous systems [20 24]. As well as paying special attention to the nature of support and catalyst, it is also important to consider the nature of the linker component connecting these two materials because the nature of the linker can have a profound effect on the activity of the catalyst. Li et al. [25] reported that the linker length was one of the most significant factors affecting the stereo selectivity of the immobilized Mn III (Salen) catalysts and suggested that the use of longer linkers would effectively highlight any confinement effects and consequently enhance the enantioselectivity exhibited by the catalyst. The use of longer axial linkers, however, could lead to a decrease in the degree of electronic communication between the support material and the Mn III (Salen) catalyst, which would have a negative effect on any enhancement in the enantioselectivity resulting from the axial linker group. Furthermore, it has been reported that longer and flexible linkers lead to an improved outcome in the bimetallic Co Salen hydrolytic kinetic resolution (HKR) reaction [26,27]. In contrast, the heterogeneous Mn III (Salen) catalysts prepared by co polymerization or grafting of long flexible linker units always provide lower ee values compared with homogeneous catalysts for the asymmetric epoxidation of olefins [28]. Mn III (Salen) complexes have recently been successfully immobilized onto MCM 41 nanopores, using a rigid phenoxyl [29] or phenylsulfide [30] group as the axial immobilization linker. It has been demonstrated that the immobilization of Mn III (Salen) through a phenoxyl group leads to a 3 fold increase in the enantioselectivity of the epoxidation of cis β ethylstyrene compared with that of its homogeneous counterpart. Furthermore, the replacement of the immobilization linker with a phenylsulfide group leads to 3.6 fold increase in the enantioselectivity of the same epoxidation reaction compared with the homogenous system. These results therefore indicate that there is a correlation between the nature of the linker group and the activity of the catalyst. To the best of our knowledge, there have been no reports in the literature pertaining to the use of tunable rigid phenoxyl linkers bearing different substituents at the o positions of the phenoxyl group to influence the activity of the Mn III (Salen) complexes towards epoxidation. Given that there is still a high level of academic interest in these materials and their potential commercial importance, there is an urgent need for the development of efficient and reusable chiral catalyst for the epoxidation of non functionalized olefins. As part of our ongoing work towards the development of novel supported catalysts for use in organic synthesis, we have prepared several ZPS PVPA supported Mn III (Salen) catalysts bearing a tunable phenoxyl linker group (Cat1 Cat3). We have also prepared a series of non supported analogues (Cat4 Cat6) for comparison, and both of these series were evaluated as catalyst for the epoxidation of olefins. The influence of different substituents at the o position of the tunable phenoxyl linker on the catalytic performance has also been evaluated both in the presence and in the absence of an axial additive. Furthermore, we have evaluated the recyclability of these catalytic systems and found that they continued to show superior levels of enantioselectivity and catalytic activity for at least five runs. We have also provided some discussion of the mechanistic pathway involved in the attack of the olefin by the Mn intermediate (i.e., Mn = v center). 2. Experimental 2.1. Materials (1S,2S) 1,2 Diaminocyclohexane, 2,4 dihydroxybenzaldehyde, α methylstyrene, indene, n nonane, N methylmorpholine N oxide (NM), chloromethyl methyl ether (toxic compound) and m chloroperbenzoic acid (m CPBA) were supplied by Alfa Aesar (Tianjin, China) and used as received without further purification. All of the other reagents chemicals used in this study were purchased as the laboratory grade from local suppliers. Styrene was distilled before use. The chiral salen ligand and Mn III (Salen) were synthesized according to the literature procedures [2] Preparation of the supports (Scheme 1) Synthesis of zirconium poly (styrene phenylvinylphosphonate) phosphate (ZPS PVPA) The synthesis and characterization of ZPS PVPA have previously been reported by our group [18,19] Synthesis of chloromethylated zirconium poly(styrene phenylvinylphosphonate) phosphate (ZCMPS PVPA) A mixture of chloromethyl methyl ether (9.30 ml), anhydrous zinc chloride (1.92 g, 14.2 mmol), and ZSP PVPA (6.00 g, 8.55 mmol) was stirred at 45 C for 8 h. The mixture was then

3 1448 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) P 3 H 2 BP EtAc/reflux P 3 H 2 H H H * C C C C * Ph H m Ph H n ZrCl 2. 8H 2 /NaH 2 P 4 THF/Reflux St PVPA St-PVPA CH 2 Cl Zr(HP 4 ) 1.35 [( 3 PCCH 2 ) n (CHCH 2 ) m ] 0.65 xh 2 ZPS-PVPA Ph H H R 2 R 1 NaH + CH 2 EtH/N 2, Reflux H L 1 R 1 = R 2 = H Ph L 2 R 1 = -CH 3, R 2 = H L 3 R 1 = -, R 2 = H S 1 H R 1 = R 2 = H S 2 R 1 = -CH 3, R 2 = H S 3 R 1 = -, R 2 = H Scheme 1. Synthetic route to the supports. CH 3 CH 2 Cl, ZnCl 2 CHCl 3, 38 o C R 1 R 2 H H ZCMPS-PVPA cooled to ambient temperature before being treated with water (20 ml) and methanol (20 ml). The mixture was then filtered and the filter cake washed sequentially with methanol and acetone before being collected and dried in vacuo to give ZCMPS PVPA in 90.3% yield. The amount of elemental chloride in the product was determined from the results of the rhombic experiments of chloromethylation. Under the optimal conditions, a chloride content of % Cl per gram of ZCMPS PVPA was obtained following the titration of this material with AgN Synthesis of supports (S1,S2, and S3) The appropriate amounts of L1, L2, and L3 were mixed with ZCMPS PVPA (2.63 g, 3.45 mmol), K2C3 (4.50 g, 30.0 mmol), and ethanol (20.0 ml) (the molar ratio of diphenol to elemental chlorine in ZCMPS PVPA was set at 5:1), respectively, and the resulting mixtures were held at 80 C for 24 h under N2. The resulting resin like products were then filtered and washed sequentially with large volumes of deionized water and ethanol to remove any residual diphenol before being dried under vacuum at 80 C to give the corresponding products in yields of 93.0%, 86.0%, and 95.0%, respectively. Following their reaction with sodium phenoxide, the residual Cl contents of the supports were obtained by titration against AgN3. The results of these titrations allowed for the number of CH2Cl groups replaced by phenoxyl groups to be conveniently calculated Preparation of the supported catalysts and non supported analogues (Scheme 2) Preparation of supported catalysts: phenoxyl modified ZCMPS PVPA Mn III (Salen) (Cat1 Cat3) A solution of chiral Mn III (Salen) (2.73 g, 4.30 mmol), phenoxyl modified ZCMPS PVPA (S1 S3), (0.50 g), and an appropriate amount of sodium hydroxide in tetrahydrofuran (50.0 ml) was stirred vigorously for 24 h under reflux. The reaction mixture was then cooled to ambient temperature and filtered to give a dark brown powder, which was washed sequentially with ethanol, CH2Cl2, and demonized water before being dried under vacuum at 80 C. The CH2Cl2 filtrate was analyzed by UV vis spectroscopy until no peaks could be detected (with CH2Cl2 as reference). The products (Cat1 Cat3) were isolated in yields of 92.0%, 89.1%, and 84.8%, respectively. The loading of the Mn III (Salen) complex in the heterogenized catalyst, based on the amount of elemental Mn, was determined to be in the range of mmol/g by AAS Preparation of non supported analogues catalysts (Cat4 Cat6) Mn III (Salen) (1.56 g, 2.56 mmol) and the appropriate amount of the linker (L4 L6,1.2 equiv.) were added to ethanol (60.0 ml), and the resulting mixture was refluxed for 5 h at 80 C (Scheme 2). The reaction was then cooled to room temperature and evaporated to dryness, the resulting residue was dissolved in CH2Cl2 and washed sequentially with deionized water and brine before being dried over anhydrous Na2S4. The solvent was then removed under vacuum to gives the desired product as a brown dark solid (Cat4 Cat6). Cat4: yield 80.0%; Anal. Calcd for Cat4 (C42H57MnN23): C 72.81%, H 8.28%, N 4.05%; Found: C 74.15%, H 8.42%, N 4.17%. Cat5: yield 76.3%, Anal. Calcd for Cat5 (C43H59MnN23): C 73.06%, H 8.41%, N 3.96%; Found: C 75.26%, H 8.63%, N 4.21%. Cat6: yield 62.7%; Anal. Calcd for Cat6 (C46H65MnN23): C 73.77%, H 8.75%, N 3.74%; Found: C 74.88%, H 8.98%, N 3.93% Characterization methods FT IR spectra were recorded on a Bruker RFS100/S spectrophotometer (Karlsruhe, Germany) as KBr disks. Diffuse reflectance UV vis spectra of the solid samples were recorded in

4 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) H R 1 CH 2 H S 1 R 1 = R 2 = H R 2 S 2 R 1 = -CH 3, R 2 = H S 3 R 1 = -, R 2 = H + THF, NaH Reflux, 24 h N N Mn Cl Jacobsen's catalyst N N Mn R 1 R 2 H CH 2 Cat 1 -Cat 3 N N Mn Cl Jacobsen's catalyst + Na EtH Reflux/N 2 N N Mn R 2 R 1 R 2 R 1 Cat 4 -Cat 6 L 4 R 1 = R 2 = H L 5 R 1 = -CH 3, R 2 = H L 6 R 1 = -, R 2 = H Scheme 2. Synthetic route to the supported and non supported analogues catalysts. the spectrophotometer with an integrating sphere using BaS4 as a reference standard. Number and weight average molecular weights (Mn and Mw) and polydispersity values (Mn and Mw) were estimated using a Waters 1515 gel permeation chromatograph (GPC) system (Massachusetts, USA) against polystyrene standards using Tetrahydrofuran (THF) as an eluent (1.0 ml/min) at 35 C. The Mn content of the catalyst was determined by TAS 986G (Beijing, China). Elemental analyses were conducted on an EATM1112 automatic elemental analyzer (Massachusetts, USA). X ray photoelectron spectra (XPS) were recorded on an ESCALAB250 system (Massachusetts, USA). Scanning electron microscopy (SEM) analysis was performed on a KYKY EM3200 system (Beijing, China). Transmission electron microscopy (TEM) analysis was conducted on a Philips TECNAI10 system (Amsterdam, Holland). Atomic force microspcopy (AFM) analysis was conducted on a NanoScope Quadrex system (NewYork, USA) Asymmetric epoxidation of unfunctionalized olefins The racemic epoxides were prepared by the epoxidation of the corresponding olefins with m CPBA in CH2Cl2, and their structures were confirmed by NMR analysis on a Bruker AV 300 system. The GC was calibrated using n nonane, as well as several olefins and the corresponding racemic epoxides. A solution of alkene (0.500 mmol), NM (338 mg, 2.50 mmol, if necessary), n nonane (internal standard, 56.0 ml, mmol), and the immobilized Mn III (Salen) complex (0.025 mmol, 5%, based on the Mn amount of the catalyst) in CH2Cl2 (3 ml) was cooled to the desired temperature. Solid m CPBA (138 mg, 0.80 mmol) was added in four portions over 2 min, and the resulting mixture was stirred at ambient temperature. Upon completion of the reaction, as indicated by TLC, the mixture was washed sequentially with saturated sodium hydroxide and brine to remove any residual m CPBA and the corresponding acid and dried over anhydrous Na2S4. The conversion and ee values were determined by GC using nonane as an internal standard. After the first run of the epoxidation reaction, the catalyst was separated by centrifugation and washed thoroughly with dichloromethane before being dried, and subjected to another cycle with fresh reactants under similar epoxidation conditions. The conversion (with n nonane as an internal standard) and the ee values were determined by gas chromatography (GC) using a Shimadzu GC2014 (Kyoto, Japan) instrument equipped

5 1450 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) with a chiral column (HP19091G B213, 30 m 0.32 mm 0.25 μm) and FID detector. The injector and detector temperatures were set at 230 C. A column temperature in the range of C was used for α methylstyrene and indene. 3. Results and discussion 3.1. FT IR spectroscopy The immobilized catalysts, as well as the homogeneous Mn III (Salen) for comparison, were characterized by FT IR spectroscopy (Fig. 1.). The FT IR spectrum of Mn III (Salen) showed characteristic vibration bands around 1620, 1535, and 569 cm 1, which were attributed to the stretching vibration modes of C=N, C, and Mn, respectively. These bands were still present in the FT IR spectra of the immobilized catalysts, which suggested that the heterogeneous catalysts had similar structures to that of neat chiral Mn III (Salen) and the structure of the catalytic active site remained intact. The stretching vibration observed at 1030 cm 1, which was assigned to the characteristic vibrations of phosphonate and phosphate in the support, was clearly weakened as a consequence of changes in the electronic structure of the host guest interaction. These observations suggested that the chiral Mn III (Salen) complex has been successfully immobilized onto the tunable phenoxyl group modified ZPS PVPA DR UV vis spectroscopy The diffuse reflectance UV vis spectra of the Mn III (Salen) complex and immobilized catalysts are shown in Fig. 2. These spectra provided further evidence in support of the successful immobilization of the Mn III (Salen) complex, based on the fact that the characteristic bands for Mn III (Salen) at 340, 435,and 510 nm had been blue shifted to 330, 410, and 505 nm, respectively, for the immobilized catalysts, which indicated the occurrence of an interaction between the Mn III (Salen) complex and the support through the tunable phenoxyl linkers. The characteristic bands at 262 and 330 nm were attributed to the charge transfer transition of the Salen ligand, whereas the bands at 410 and 505 nm were attributed to the ligand to metal charge transfer transition and d d transition of the Mn III (Salen) complex [31]. Transmittance (4) (3) (2) (1) Wavenumber (cm 1 ) Fig. 1. FT IR spectra of Mn III (Salen) (1), Cat1 (2), Cat2 (3), and Cat3 (4). Absorbance Wavelength (nm) 3.3. Microscopic analysis (3) (2) Fig. 2. DR UV vis spectra of Mn III (Salen) (1), Cat1 (2), Cat2 (3), and Cat3 (4). SEM, TEM, and AFM images of the immobilized Mn III (Salen) catalyst (Cat3) are shown in Fig. 3. The SEM image of the particles of the Cat3 catalyst indicated that they were submicron in diameter. The SEM image also showed that Cat3 was in a loose, amorphous state. Numerous cavities, holes, and pores of different sizes and shapes also existed on the surfaces of the particles. The TEM and AFM images revealed that the particles of (1) (4) (a) (b) (c) Fig. 3. SEM (a), TEM (b), and AFM photographs (c) of immobilized catalyst Cat3.

6 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) the Cat3 catalyst consisted of much smaller particles. The images indicated that the surface properties of the catalyst would lead to an increase in the surface area of the catalyst and allow the substrates better access to the catalytically active sites X ray photoelectron spectroscopy XPS has been used extensively to obtain detailed information about the state of metal species immobilized on the surfaces of catalyst in terms of allowing for the electronic properties of these species to be effectively investigated. Fig. 4. shows the Mn 2P3/2 XPS spectra of the Mn III (Salen) complex and the immobilized catalyst (Cat3). The shift in the binding energy of the major peak from to ev was attributed to Mn 2p3/2 following the immobilization process, which is in agreement with the values previously reported for Mn III (Salen) and porphyinic ligands [32,33]. The observed increase of 0.3 ev in the chemical shift for the immobilized salen complex comparing with Mn III (Salen) was attributed to differences in the coordination environment of Mn Catalytic properties of the immobilized catalyst Asymmetric epoxidation of unfunctionalized olefins The catalytic activities and enantioselectivities of the catalysts (Cat1 Cat6) were evaluated for the asymmetric epoxidation of unfunctionalized olefins in CH2Cl2 using m CPBA as an Intensity Binding energy (ev) oxidant. All of the reactions proceeded smoothly with the heterogeneous catalysts showing higher ee values but slightly lower levels of conversions compared with the corresponding homogeneous Jacobsen s catalyst under the same conditions. Table 1 shows that Jacobsen s catalyst and the non supported analogues (Cat4 Cat6) were active and enantioselective for the epoxidation of α methylstyrene although the enantioselectivities were not very high (49.5% 52.0%). After anchoring the Jacobsen s catalyst onto the ZPS PVPA using phenoxyl linkers of varying steric hindrance, there was a clear reduction in the activities of these heterogeneous catalysts (Cat1 Cat3) for the (1) (2) Fig. 4. XPS spectra of Mn III (Salen) (1) and Cat3 (2). Table 1 Asymmetric epoxidation of alkenes catalyzed by Cat1 Cat6 with m CPBA as oxidants. Entry Substrate Catalyst xidant Conversion a (%) Selectivity a (%) ee b (%) 1 Jaco m CPBA/NM c 2 Cat4 m CPBA/NM c 3 Cat5 m CPBA/NM c 4 Cat6 m CPBA/NM c 5 Cat6 m CPBA c 6 Cat1 m CPBA/NM c 7 Cat1 m CPBA c 8 Cat2 m CPBA/NM c 9 Cat2 m CPBA c 10 Cat3 m CPBA/NM c 11 Cat3 m CPBA c 12 Jaco m CPBA/NM d 13 Cat1 m CPBA d 14 Cat2 m CPBA d 15 Cat3 m CPBA d 16 Cat3 m CPBA e 17 Jaco m CPBA/NM f 18 Cat1 m CPBA f 19 Cat2 m CPBA f 20 Cat3 m CPBA f Reactions were carried out at 0 C for 60 min in CH2Cl2 (3 ml) with alkene (0.5 mmol) NM (337.5 mg, 2.5 mmol, if necessary), n nonane (internal standard, 56 μl, 0.5 mmol), and immobilized Mn III (Salen) complexes (0.025 mmol, 5.0 mol%). a Determined by GC by integration of product peaks against an internal quantitative standard (n nonane), correcting for response factors. b Determined by GC with a chiral capillary column (HP 19091G B233, 30 m 0.32 mm 0.25 μm). c Epoxide configuration S. d Epoxide configuration S. e Reactions were carried out at 78 C for 90 min and epoxide configuration S. f Epoxide configuration 1S, 2R.

7 1452 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) epoxidation of α methylstyrene under the same conditions. Interestingly, however, there was a notable difference in the ee value, which increased from 52% to 73.2% for Cat3 towards the epoxidation of α methylstyrene. Li et al. [29] reported that the ee values increased from 56% to 72% for the epoxidation of α methylstyrene following the immobilization of Mn III (Salen) onto the surface of MCM 41 via the oxygen atoms of the phenoxyl group although the conversion remained low at only 60%. This increase in the ee has been mainly attributed to the axial phenoxyl linkers and the support [34]. These slight decreases in conversion are most likely due to the slow diffusion of the reactant and the oxidant within the microporous channels and secondary channels of ZSP PVPA. However, following the immobilization process, there was a reduction in the selectivity of the product, which was mainly attributed to the exothermic activity associated with the dissolution of the m CPBA and the acidic conditions, which could have contributed to the ring opening of the epoxides. The heterogenized catalysts also showed good catalytic activity and enantioselectivity towards bulkier olefins, such as indene (98.9% conversion; 80.1% ee), which indicated that the active sites in the microporous channels of ZPS PVPA could also be readily accessed by bulkier reactants. When styrene was used as substrate, the reaction gave low ee values in the range of 12.9% 38.6%. However, when the reaction temperature was lowed from 0 to 78 C, the enantioselectivity of the Cat3 catalyst towards the epoxidation of styrene improved significantly from 38.6% to 56.2% ee. A comparison of Cat3 and Jacobsen s catalyst with a previously reported catalyst [19] for the epoxidation of styrene revealed that these systems provided increases in the reported ee values of 9.2% and 12.8%, respectively, under the same conditions The effect of axial ligands NM Table 1 shows a comparison of the results obtained for the enantioselective epoxidation of α methylstyrene in the presence/absence of axial bases of NM using Jacobsen s catalyst and the non supported analogues (Cat4 Cat6). It is clear from the results reported previously in homogeneous systems that the addition of an axial additive such as NM induces a conformational change in the skeleton of the Mn III (Salen) complex, resulting in an increase in the reaction rate and an improvement in the enantioselectivity [21 23]. Interestingly, slight increases were observed in the ee values in the current study for the epoxidations catalyzed by Mn III (Salen) bearing axially coordinated phenoxyl linkers of varying steric hindrance. For example, the ee value for the epoxides of α methylstyrene increased from 51.1% to 58.5% without the addition of NM (Table 1, entry 4 vs 5), and similar results have also been reported by List et al. [35] and Huang et al. [36], where Mn III (Salen) was axially coordinated to rigid phosphate and diphenolate groups, which replaced the Cl atoms in the Mn III (Salen) complex. The heterogeneous catalysts (Cat1 Cat3) also displayed high ee values and conversions in the absence of the NM additive, which is commonly used to improve the catalytic activity. From a practical perspective, the addition of NM to the reaction mixture did not lead to an improvement in asymmetric induction but resulted in a significant reduction in the ee values and reactivity. The ee value for the epoxidation of α methylstyrene increased from 6.8% to 76.8% without the addition of NM. This phenomenon has been reported previously by our group, where it was attributed to the organic polymer inorganic hybrid support ZPS PVPPA and the axially coordinating phenoxide group [19]. In the current study, this novel catalytic result was induced by another important factor, namely the steric hindrance effect derived from the ortho substituents of the tunable phenoxyl axial linkers. It was envisaged that the use of tunable phenoxyl axial linkers with substituents bearing structures similar to those of the N oxide ligand would behave effectively as axial ligands. Thus, the addition of an N oxide ligand led to the occurrence of steric hindrance effects, which resulted in changes to the optimal geometric configuration of the reactive intermediate or transition states of salen Mn v =. These changes then led to a decrease in the chiral recognition properties of the catalytic system and the observed lower enantioselectivity The effect of solvents on the styrene Table 2 shows a comparison of the enantioselective epoxidation of styrene using the Cat3 catalyst in various solvents. As expected, the use of different solvents had a pronounced effect on the catalytic activity and enantioselective. The results of this study revealed that dichloromethane was the optimal solvent for the reaction, providing a yield of 72.09% and an ee of 38.6%. In contrast, the use of hexane and alcohol resulted in yields of 3.71 and 4.30% and ee values of 9.6 and 13.5%, respectively. These differences among the solvents were attributed to the fact that Cat3 swelling to a much greater extent in dichloromethane than any other solvent. The enantioselectivity was lower in ethyl acetate, acetonitrile and acetone than it was in dichloromethane, indicating that solvents containing oxygen and nitrogen atoms bearing lone pairs of electrons could be coordinating to the metal center of the chiral Mn III (Salen) complex and suppressing the formation of the active oxygen transfer species (Mn V oxo) required for the epoxidation of styrene. The ee of the reaction in acetonitrile was particularly low at only 24.8% The steric hindrance effect originated in the tunable phenoxyl linkers for the homogeneous and heterogeneous epoxidation system The steric hindrance effect of the tunable phenoxyl linkers Table 2 Asymmetric epoxidation of styrene catalyzed by Cat3 in different solvents. Entry Solvent Conversion (%) Selectivity (%) ee a (%) 1 n Hexane Ethanol Dichloromethane Acetone Acetonitrile Ethylacetate Reactions were carried out at 0 C for 60 min in CH2Cl2 (3 ml) with alkene (0.5 mmol), n nonane (internal standard, 56 μl, 0.5 mmol), and immobilized Mn III (Salen) complexes (0.025 mmol, 5.0 mol%). a Epoxide configuration S.

8 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) on the epoxidation of unfunctionalized alkenes was also evaluated, and Table 1 shows a comparison of the supported and non supported catalysts in terms of their epoxidation of unfunctionalized alkenes under similar conditions. When the α methylstyrene was used as substrate, the ee values of the resulting epoxides were found to be in the range of 49.5% 51.1%, with conversions in the range of 97.2% 98.0%. These values were obtained after the Cl atoms were replaced with a series of different phenoxyl linker groups, which suggested that the steric hindrance effects of the linker were not having a discernible impact on the homogeneous reaction results. However, the use of the heterogeneous catalyst Cat3 led to much higher ee values (up to 76.8%), which were 9.5% and 3.6% higher than those achieved with Cat1 and Cat2, respectively. With regard to the conversions, there was a slightly decrease going from 98.8% to 90.7%. Similar results were also obtained for styrene and indene. When the phenoxyl group on the linker was replaced with an o t Bu group, the enantioselectivity of the epoxidation of α methylstyrene increased from 6.8% to 76.8%, representing increases of 9.0% and 2.3% compared with the results for Cat1 and Cat2, respectively. These results demonstrated that the substituents at the o positions of the tunable phenoxyl linkers have a critical impact on the catalytic activity, in that the o t Bu group provided higher levels of enantioselectivity than the o H and o CH3 groups of the phenoxyl linker. These results therefore indicated that pathway (a) (Scheme 3) provided the most accurate representation of the way in which the Mn= v center reacts with the olefin. In principle, there are five possible trajectories ((a) (e) in Scheme 3) for the reaction of the olefin with the Mn= v center, which have been reported by Jacobsen et al. [37] and Hosoya et al. [38]. None of the other possible reaction pathways could account the different catalytic results observed for the linkers bearing different substituents at their o positions. Furthermore, it has been reported that good yields and ee values for the epoxides can be achieved by adjusting the properties of 3,3 phenyl groups in Scheme 3. Hence, we believe that pathway (a) represents one of the best pathways for rationalizing the results observed in the current study. More detailed studies concerning the mechanistic behavior of these supported and non supported analogues are currently in underway in our laboratory. (c) (a) (d) (e) H H N N Mnv 3 3' R2 R 1 Support (b) Scheme 3. The passway of olefins attack to Mn= v center. (a) Table 3 The recycling of immobilized catalyst Cat3 in the asymmetric epoxidation of α methylstyrene with m CPBA oxidant. Run Conversion (%) Selectivity (%) ee a (%) Reactions were carried out at 0 C for 60 min in CH2Cl2 (3 ml) with alkene (0.5 mmol), nonane (internal standard, 56 μl, 0.5 mmol), and immobilized Mn III (Salen) complexes (0.025 mmol, 5.0 mol%). a Epoxide configuration S The recycling of the supported chiral Mn III (Salen) catalyst The recyclability of the immobilized catalyst Cat3 was evaluated using the epoxidation of α methylstyrene as a model reaction. After the first run of the epoxidation reaction, the catalyst was separated by centrifugation. The separated catalyst was then collected and washed thoroughly with dichloromethane before being dried and subjected to another cycle with fresh reactants under similar epoxidation conditions (i.e., the same ratio of the substrate to catalyst and solvent to catalyst). The recovery of the catalyst after each run was found to be in the range of 93% 98%. As shown in Table 3, there were no significant changes in the catalytic activity and enantioselectivity exhibited by the catalyst after five runs, and no leaching of Mn into the filtrate was observed by AAS or UV vis, which indicated that the chiral Mn III (Salen) complex was strongly bonded to the tunable phenoxyl modified ZPS PVPA support. Considering the gradual reduction in the conversion and ee values of the catalyst following several runs, the immobilized Cat3 catalyst was subjected to a Soxhlet extraction procedure using dichloromethane after six reaction cycles. This extraction process led to an increase in the conversion (86.5% vs 82.5%) in the seventh run (entry 7), which indicated that the catalyst had remained intact and that the observed reduction in activity was related to the blockage of active sites during the previous runs. After the Cat3 catalyst had been recycled 10 times, the Mn content of the heterogeneous catalyst had decreased by 78.0% compared with the total amount of Mn (0.41 mmol/g). The observed decreases in the activity as the number of cycles increased was therefore attributed to the leaching of the metal complex from the support. 4. Conclusions We have developed a series of chiral Mn III (Salen) catalysts that were axially supported onto zirconium poly(styrene phenylvinylphosphonate) phosphate (ZPS PVPA) through phenoxyl linkers of varying steric hindrance, and evaluated their performance as catalysts for the epoxidation of a variety of un

9 1454 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) Graphical Abstract Chin. J. Catal., 2014, 35: doi: /S (14) Chiral Mn III (Salen) supported on tunable phenoxyl group modified zirconium poly (styrene phenylvinylphosphonate) phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins Xiaochuan Zou *, Kaiyun Shi, Cun Wang Chongqing University of Education; Southwest University R 1 R 2 R 4 R 3 + xidant catalyst R 1 R 2 * * R 4 R 3 We have reported for the first time that the use of tuneable rigid phenoxyl linkers bearing ortho substituents imposing different steric hindrance effects has a critical effect on the catalytic activity of the supported systems towards the epoxidation of olefins, especially heterogeneous epoxidation systems. N N Mn R 5 R 6 H functionalized olefins. Significant increases were observed in the activities and enantioselectivities of these catalysts over the corresponding heterogeneous catalysts such as Jacobsen s catalyst and their non supported analogues. The reactions were conducted in the absence of NM in CH2Cl2 using m CPBA as an oxidant. Furthermore, the catalysts could be recycled up to five times without any significant reduction in their catalytic activity or enantioselectivity. The influence of the steric hindrance effect derived from the tunable phenoxyl linkers used in the homogeneous and heterogeneous epoxidation systems was explored at length, and the results demonstrated that variations in the steric hindrance imposed by the phenoxyl linker had a significant effect on the catalytic activity and enantioselectivity. Further studies aimed at comparing the effect of different linker groups on the catalytic activities of these systems towards different reactions would therefore pave the way for the rational design of highly active and selective supported catalysts. References [1] Kamata K, Yonehara K, Sumida Y, Yamaguchi K, Hikichi S, Mizuno N. Science, 2003, 300: 964 [2] Zhang W, Loebach J L, Wilson S R, Jacobsen E N. J Am Chem Soc, 1990, 112: 2801 [3] Heitbaum M, Glorius F, Escher I. Angew Chem Int Ed, 2006, 45: [4] Baleizo C, Garcia H. Chem Rev, 2006, 106: 3987 [5] Fraile J M, Garcia J I, Mayoral J A. Chem Rev, 2009, 109: 360 [6] Xu G J, Wei S L, Fan Y G, Zhu L B, Tang Y H, Zheng Y S. Chin J Catal ( 徐国津, 魏赛丽, 樊颖果, 朱丽波, 唐玉海, 郑元锁. 催化学报 ), 2012, 33: 473 [7] Breinbauer R, Jacobsen E N. Angew Chem Int Ed, 2000, 39: 3604 [8] Tian P, Gao B J, Chen Y J. Chin J Catal ( 田鹏, 高保娇, 陈英军. 催化学报 ), 2011, 32: 483 [9] Notestein J M, Katz A. Chem Eur J, 2006, 12: 3954 [10] Ye Y J, Huang J W, Cai J H, Wu W H, Yu H C, Zhou X T, Ji H B, Ji H N. Chin J Catal ( 叶元坚, 黄锦汪, 蔡金华, 吴文海, 余汉城, 周贤太, 纪红 兵, 计亮年. 催化学报 ), 2010, 31: 1507 [11] Zheng X L, Jones C W, Weck M. J Am Chem Soc, 2007, 129: 1105 [12] White D E, Jacobsen E N. Tetrahedron: Asymmetry, 2003, 14: 3633 [13] Bai R F, Fu X K, Bao H B, Ren W S. Catal Commun, 2008, 9: 1588 [14] Ren W S, Fu X K, Bao H B, Bai R F, Ding P P, Sui B L. Catal Commun, 2009, 10: 788 [15] Ren W S, Fu X K. J Mol Catal A, 2009, 312: 40 [16] Zou X C, Shi K Y, Chen S C, Fu X K. Chem J Chin Univ ( 邹晓川, 石开云, 陈绍成, 傅相锴. 高等学校化学学报 ), 2013, 34: 2319 [17] Zou X C, Chen S C, Ren Y R, Shi K Y, Li J, Fu X K. Sci China Chem, 2012, 55: 2396 [18] Gong B W, Fu X K, Chen J X, Li Y D, Zou X C, Tu X B, Ma L P. J Catal, 2009, 262: 9 [19] Zou X C, Fu X K, Li Y D, Tu X B, Fu S D, Luo Y F, Wu X J. Adv Synth Catal, 2010, 352: 163 [20] Palucki M, Pospisil P J, Zhang W, Jacobsen E N. J Am Chem Soc, 1994, 116: 9333 [21] Nowak D M, Lansbury P T. Tetrahedron, 1998, 54: 319 [22] Palucki M, McCormick G J, Jacobsen E N. Tetrahedron Lett, 1995, 36: 5457 [23] Wang D P, Wang M, Wang X N, Chen Y G, Gao A P, Sun L C. J Catal, 2006, 237: 248 [24] Kureshy R I, Ahamd I, Khan N H, Abdi S H R, Singh S, Pandia P H, Jasra R V. J Catal, 2005, 235: 28 [25] Malek K, Li C, van Santen R A. J Mol Catal A, 2007, 271: 98 [26] Zheng X L, Jones C W, Weck M. Adv Synth Catal, 2008, 350: 255 [27] Minutolo F, Pini D, Petri A, Salvadori P. Tetrahedron: Asymmetry, 1996, 7: 2293 [28] Zhang H D, Zhang Y M, Li C. Tetrahedron: Asymmetry, 2005, 16: 2417 [29] Xiang S, Zhang Y L, Xin Q, Li C. Chem Commun, 2002: [30] Zhang H D, Xiang S, Li C. Chem Commun, 2005: 1209 [31] Lou L L, Yu K, Ding F, Peng X J, Dong M M, Zhang C, Liu S X. J Catal, 2007, 249: 102 [32] Domenech A, Formentin P, Garcia H, Sabater M J. Eur J Inorg Chem, 2000:1339 [33] Li Z, Xia C G, Zhang X M. J Mol Catal A, 2002, 185: 47 [34] Han D F, Yang Q H, Li C. Chin J Catal ( 韩涤非, 杨启华, 李灿. 催化学报 ), 2008, 29: 789 [35] Liao S H, List B. Angew Chem Int Ed, 2010, 49: 628

10 Xiaochuan Zou et al. / Chinese Journal of Catalysis 35 (2014) [36] Huang X M, Fu X K, Wu X J, Jia Z Y. Tetrahedron Lett, 2013, 54: 4041 [37] Jacobsen E N, Zhang W, Muci A R, Ecker J R, Deng L. J Am Chem Soc, 1991, 113: 7063 [38] Hosoya N, Hatayama A, Irie R, Sasaki H, Katsuki T. Tetrahedron, 1994, 50: 4311 可调苯氧基修饰的聚 ( 苯乙烯 - 苯乙烯基膦酸 )- 磷酸氢锆固载手性 Mn III (Salen) 高效催化烯烃环氧化 邹晓川 a,b,*, 石开云 a a, 王存 a 重庆第二师范学院生物与化学工程系, 重庆 b 西南大学应用化学研究所, 重庆市应用化学重点实验室, 三峡库区生态环境教育部重点实验室, 重庆 摘要 : 使用不同空间位阻的苯氧链接手臂修饰的聚 ( 苯乙烯基 - 苯乙烯膦酸 )- 磷酸氢锆轴向固载手性 Mn III (Salen) 催化剂 (Cat 1 Cat 3 ), 随后在间氯过氧苯甲酸 (m-cpba) 为氧化剂的体系中考察了固载催化剂的催化性能. 同时, 在相同氧化体系下测试了一系列均相催化剂类似物 (Cat 4 Cat 6 ). 结果表明, 在非均相条件下, 可调变苯氧链接手臂的邻位取代基对催化剂活性起着重要作用, 环氧化产物的对映选择性随着取代基位阻的增加而增大, 但产物转化率有一定程度下降. 此外, 非均相催化剂即使在没有轴向助剂的参与下 ( 通常需要添加, 为了增大催化活性 ) 仍然表现出非常高的催化活性, 尤其对 α- 甲基苯乙烯反应, 其对映选择性从 6.8% 增加到 76.8%, 转化率从 19.8% 上升到 90.7%. 制备的非均相催化剂 11 次的循环使用实验表明, 在前 5 次使用后催化剂活性与对映选择性没有明显变化. 关键词 : 聚 ( 苯乙烯基 - 苯乙烯膦酸 )- 磷酸氢锆 ; 手性 Jacobsen 催化剂 ; 可调变苯氧链接基团 ; 不对称非均相环氧化 收稿日期 : 接受日期 : 出版日期 : * 通讯联系人. 电话 : (023) ; 传真 : (023) ; 电子信箱 : zxcvip2003@163.com 基金来源 : 重庆市基础与前沿研究计划 (cstc2013jcyja50013); 重庆市教委科学技术研究项目 (KJ131504); 重庆高校创新团队建设计划 (KJTD201325). 本文的英文电子版由 Elsevier 出版社在 ScienceDirect 上出版 (

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