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Supported BINAP-M Catalysts

Wenqing Yang , Dale Xie , Jun Cheng , Weike Tang , Ruobing Wang , Yisi Feng

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (10) : 1706 -1720.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (10) : 1706-1720 DOI: 10.7536/PC200813
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Supported BINAP-M Catalysts
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Abstract

As one of the most important and well-known chiral catalysts, 1,1'-binapthyl-2,2'-bisdiphenylphosphine metal complexes(BINAP-M) have been widely concerned in industry and basic theoretical research in the past few decades. Although BINAP-M as a homogeneous chiral catalyst has the characteristics of high activity and good selectivity, it also has the limitations of high price, high application cost and difficult to recycle, especially the catalyst residues in synthesis products such as pharmaceutical products, which limits its large-scale application in industry. Therefore, it has become an important research topic to search for BINAP-M catalysts which can not only keep high catalytic activity, but also be easy to recover and recycle. In this paper, the research progress of recyclable BINAP-M catalysts in recent years is summarized. The research results of adsorption-supported and covalently-supported BINAP-M catalysts in the field of recyclability are mainly introduced. The advantages and disadvantages of different types of recyclable BINAP-M catalysts are analyzed and discussed. On this basis, a covalently-supported BINAP-M catalyst with “flexible bridge chain” structure is also introduced, and its application prospect in “quasi-homogeneous” catalytic reaction is analyzed, which provides a new research idea for the design and preparation of supported catalyst.

Contents

1 Introduction

2 BINAP directly supported catalyst

2.1 Oxide supporter loading

2.2 Magnetite nanoparticle supporter loading

2.3 Other supporter loading

3 Covalently loaded BINAP-M catalyst

3.1 Mesoporous silica covalent loading

3.2 Polymer supporter loading

3.2.1 Conventional polymer supporter

3.2.2 Dendrimer supporter

3.2.3 Porous polymer supporter

3.3 Other supporter loading

4 Conclusion and outlook

Graphical abstract

Keywords

BINAP-M / covalent loading / adsorption loading / quasi-homogeneous catalysis / flexible bridge chain

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Wenqing Yang, Dale Xie, Jun Cheng, Weike Tang, Ruobing Wang, Yisi Feng. Supported BINAP-M Catalysts. Progress in Chemistry, 2021, 33(10): 1706-1720 DOI:10.7536/PC200813

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1 Introduction

Transition metal complex catalysts are the most widely studied and applied homogeneous catalysts in green organic synthesis chemistry, which are often used in various organic synthesis reactions because of their mild reaction conditions, high catalytic activity, good selectivity, and strong controllability of catalyst design and preparation process[1,2]. Among that transition metal complex catalyst, ligands contain N and P are the most common, among which Noyori et al. First reported 2, 2 '-bis (diphenylphosphino) -1, 1' -binaphthyl (BINAP for short, as shown in scheme 1) in 1980 as the most famous -axis chiral ligand,BINAP-M can coordinate with a variety of metal ions or metal nanoparticles (represented by BINAP-M) to form a homogeneous catalyst, which can be used as a chiral catalyst to catalyze various asymmetric hydrogenation reactions with high efficiency and high selectivity, thus opening up the research direction of BINAP- M catalysis[3][4]. Among the reported BINAP-M catalysts, BINAP-Pd and BINAP-Ru are the most representative chiral homogeneous catalysts, which have been widely used in various fields of chiral catalysis[5⇓⇓⇓⇓⇓~11].
BINAP-M has not only achieved fruitful results in the theoretical research of organic synthesis reactions, but also been applied in practical industrial production, showing obvious economic benefits[4]. For this work, Noyori was awarded the Nobel Prize in Chemistry in 2001.
Although BINAP-M catalyst has excellent catalytic performance, it is usually used in a large amount in the reaction process, generally 1 mol% ~ 10 mol% of the reaction substrate, which is expensive and difficult to recycle, resulting in high use cost. In addition, in the most widely used production fields of BINAP-M, such as medicine and food additives, there are strict restrictions on the impurity content in the product, and cumbersome post-treatment processes are needed to remove metal components and ligand residues in the product, which leads to a decrease in product yield and a sharp increase in production costs. In recent years, in order to solve the recycling defects of BINAP-M catalyst in practical application, a variety of BINAP-M recovery technologies have been developed, such as nanofiltration separation technology, reaction-controlled phase transfer catalysis technology, membrane separation technology, silica gel adsorption method and fluorine two-phase technology[12][13][14][15][16]. Although the existing technologies and methods have their own advantages, these homogeneous catalyst recovery technologies still have their own limitations, and it is difficult to achieve industrial application. Therefore, it is of great theoretical significance and application value to study the recyclable BINAP-M catalyst.
Studies at home and abroad have shown that the most effective way to separate and recycle BINAP-M is immobilization, that is, using various organic, inorganic or composite materials as carriers, through adsorption, covalent grafting and ionic bonding, BINAP-M is immobilized on the carrier to prepare various supported catalysts[17]. In this paper, the research progress of different types of recyclable supported BINAP-M in recent years is summarized, and the development prospect of this field is analyzed and prospected.

2 Adsorption supported BINAP catalyst

Adsorption-supported catalysts are one of the most simple and effective recyclable catalysts. BINAP-M is adsorb on that surfaces of various carrier through van der Waals force, electrostatic action, hydrogen bonding action or ionic charge action, for example, the BINAP-M is adsorbed and load on carriers such as silicon dioxide, aluminum oxide, inorganic clay, metal nanoparticles and the like to obtain the BINAP-M direct load type catalyst, so that the catalytic performance of the BINAP- M can be retained, and recycling is convenient[18].

2.1 Oxide carrier load

Inorganic materials such as montmorillonite, hydrotalcite and silica are the most common and widely used catalyst carriers at present, which are cheap and stable in performance. Shimazu et al. exchanged the sodium ion in the hydrophobite with the ligand [ ((S)-binap)Rh(cod)]+) cation in the mixed solvent of acetonitrile and water by ion exchange method to prepare the hydrophobite-supported binap-M catalyst, which was applied to the asymmetric hydrogenation of α, β-unsaturated carboxylic esters with different chain lengths[19]. The experimental results showed that the enantioselectivity of the R isomer of methyl succinate was 66% ee when dibutyl itaconate was used as substrate. It was found that the enantioselectivity of the catalyst increased with the decrease of the dielectric constant of the reaction solvent. In addition, in the presence of ethanol and cyclohexane, the steric hindrance between the ester group and the BINAP phenyl group may affect the contact frequency between the substrate and the active site of the catalyst, thus improving the asymmetric selectivity of the catalyst.
Wang et al. designed and prepared [Cu(binap)I]2@HT(HT: hydrotalcite] supported catalyst (as shown in Figure 2) for hydrogen transfer reaction and dehydrogenation reaction by loading BINAP-Cu complex on hydrotalcite by impregnation method with hydrotalcite as carrier[20]. When the substrates were aromatic amine and benzyl alcohol and the loading of active component was 5% or 10%, the catalyst showed good catalytic activity and the yield could reach 85%. The catalyst [Cu(binap)I]2@HT can be reused for more than 5 times in solvent-free or aqueous solution. According to ICP analysis, the loss of P element in the catalyst after 5 cycles is about 0.35%, which proves that the catalyst has good stability.
In addition, Wang et al. Expanded the application scope of the catalyst [Cu(binap)I]2@HT, and used it to catalyze the tandem reaction of carbon-sulfur bond cross-coupling and carbon-hydrogen bond hydroxylation between benzenethiol and phenylboronic acid, which showed excellent catalytic activity and wide substrate adaptability. When the loading of active component reached 10%, the yield of the model reaction reached the optimum (67%)[21]. Catalyst 2 was washed and filtered by centrifugal water, and then recycled for 5 times under the optimal reaction conditions (90 ℃, 12 H), with no significant reduction in catalytic efficiency and a yield of 59%. In the two catalytic systems, the [Cu(binap)I]2@HT catalyst showed good stability and substrate adaptability, which indicated that the layered structure of hydrotalcite could protect the active components of the catalyst and maintain high catalytic efficiency under different reaction conditions.
Fern Fernández et al. Used montmorillonite (MK-10T) and bentonite (Na+-MT) as carriers respectively.The MK-10T-BINAP-Rh catalyst is prepared by loading (R)-BINAP-RhX-(X-=BF4, PF4, SO3CF3, BPh4) on a carrier through an ion exchange method[22]. The supported catalyst is applied to catalyzing the asymmetric hydroboration/oxidation reaction of aryl ethylene (shown as a scheme 3) and shows good catalytic activity, the yield of the product 1-phenylethanol reaches 96%, and the enantioselectivity reaches 55% ee. It was also found that when the catalyst was recycled twice, it showed better catalytic efficiency, and the yield and enantioselectivity of 1-phenylethanol were comparable to those of the corresponding homogeneous catalyst, which were 99% and 60% ee, respectively. The catalyst can still maintain good catalytic efficiency after three cycles.
In 2000, Anderson et al. Prepared a mesoporous silica material (HMS) with a pore size of 2.6 nm, and embedded the catalyst Ru-BINAP into the pores of mesoporous silica by impregnation and adsorption to obtain the mesoporous silica-supported catalyst HMS-Ru-BINAP[23]. The catalyst shows high catalytic activity for the selective hydrogenation of carbon-carbon double bonds of alpha, beta-unsaturated carboxylic acids, such as alpha-acetylaminocinnamic acid and itaconic acid, in an aqueous phase reaction (as shown in a scheme 4). When the substrate is (Z) -2-acetamido-3-phenylacrylic acid (sodium salt), the catalytic conversion rate can still reach more than 80% after the catalyst is recycled for three times, and the enantioselectivity of R-acetylphenylalanine can still maintain more than 40% ee. When the substrate is itaconic acid, the catalytic conversion can be as high as more than 90% after the catalyst is recycled for three times, but the enantioselectivity for S-configuration 2-methylsuccinic acid is only about 15% ee.
A mesoporous silica with large cavities was prepared by using tetraethoxysilane (TEOS) as the silica source, nonionic block copolymer F127(EO106PO70EO106,EO polyethylene oxide and polypropylene oxide) as the template, and 1,3,5-trimethylbenzene and inorganic salts as the additives. The mesoporous silica with face-centered cubic lattice (Fm-3m) (C-FDU-12) was obtained by calcining the silica at 550 ℃ under N2[24]. C-FDU-12 can be used as a mesoporous silica-based nanoreactor, and reactants and catalysts can move freely in the reactor, which maximally promotes the full contact between the catalyst and the substrate, protects the active components, and simultaneously reduces the influence of the carrier on the activity of the catalyst. In 2015, Yang et al. First injected the Noyori catalyst RuCl2(R-binap)(dmf)n into the C-FDU-12 reactor, and then used an active chlorosilane reagent to reduce the inlet size of the C-FDU-12 reactor, thus preparing the catalyst Ru- (R-Binap) @ C-FDU12 (as shown in Figure 5)[25]. It was proved that the molecular catalyst could move freely in the nanoreactor by the characterization of 31P and nuclear magnetic resonance. Using methyl acetoacetate as the substrate, the conversion rate of catalytic hydrogenation reached an astonishing 99%, and the TOF value reached a 299 h-1. The amount of catalyst in the nanoreactor was screened and it was found that the optimal enantioselectivity of 97.3% ee was achieved when the Ru loading reached 0.5 wt%. It was also found that with the increase of metal loading in C-FDU-12 (0.12 wt% ~ 0.82 wt%), the TOF value of the reaction decreased (299~82 h-1). The results showed that the space microenvironment in the C-FDU-12 nanocages was very important, and the low loading was conducive to the diffusion of reactants and catalysts, thus improving the catalytic efficiency.
Although oxide is the most common carrier, it is not resistant to acid and alkali and easy to corrode, which makes it easy to lose its reactivity under harsh reaction conditions. Moreover, the abundant polar groups on the surface of the support have a great influence on the catalytic activity of BINAP-M. Therefore, the successful industrial application of this kind of catalyst is rarely reported.

2.2 Magnetic nanoparticle carrier load

Functionalized magnetic nanoparticles are a kind of special catalyst carriers which have attracted much attention in recent years. In the process of use, the catalyst can be quickly separated from the reaction system by applying an external magnetic field environment. Nanoparticles have higher specific surface area (for example, a sphere with a diameter of 10 nm corresponds to a theoretical surface area of 600 m2·cm-3), which can provide more catalyst immobilization sites and increase the loading of active components of the catalyst, thereby improving the catalytic efficiency of the supported heterogeneous catalyst. Magnetic nanoparticles have low toxicity and do not need any expensive, toxic and redundant ligands in the preparation process, which makes them a hot research direction of catalyst support in recent years[26].
Lin et al. Proposed a strategy to achieve catalyst loading on the surface of magnetic nanoparticles by coordinating with phosphate on BINAP[27,28]. That is, the magnetic nanoparticle Fe3O4 is used as a carrier, and Ru-Cl-DPEN-BINAP (DPEN: 1,2-diphenylethylenediamine) modified by a 4-site or 4,4 '-site phosphate group is respectively loaded on the surface of the magnetic nanoparticle by an ultrasonic adsorption method to prepare the chiral supported catalyst Fe3O4-Ru-Cl-DPEN-BINAP (as shown in Figure 6). The phosphate radical on the active component has strong interaction with the Fe3O4 nanoparticles, which is favorable for loading the active component on the magnetic Fe3O4 nanoparticle carrier. Aromatic ketone is used as a substrate, and a magnetic nanoparticle-supported Ru catalyst 5 or 6 is used as a catalyst for carrying out asymmetric hydrogenation reaction to obtain chiral aromatic secondary alcohol. Catalyst 5 could be reused for 14 times with 99% conversion and 96.7% ee. The conversion and enantioselectivity of catalyst 6 were 100% and 98.1% ee, respectively. After a simple magnetic precipitation separation, the catalyst can be reused for 9 times, and the catalytic conversion and enantioselectivity can still reach 100% and 98. 0% ee, showing excellent recycling performance.
Yamashita et al. prepared FePd magnetic nanoparticles (with an average diameter of 5.6 nm) by a conventional thermal decomposition reduction method, dispersed them into a toluene solvent, added a chiral BINAP ligand to the solvent, and promoted the BINAP to coordinate with FePd by heating to prepare a magnetic nano-chiral catalyst FePd- (S) -BINAP or FePd- (R) -BINAP (as shown in Figure 7)[29]. FePd- (S) -BINAP or FePd- (R) -BINAP catalyzed asymmetric Suzuki-Miyaura coupling reaction using 1-bromo-2-methoxynaphthalene and naphthylboronic acid as substrates to give (S) -binaphthyl in 99% yield with 48% ee enantioselectivity. The catalyst can be separated from the reaction mixture under the external magnetic field, which provides a simple way for the separation of the catalyst. In addition, the FePd nanoparticles not only serve as a magnetic nanoparticle carrier, but also serve as a catalytically active metal component, so that the FePd nanoparticles are a supported catalyst integrating an active component and a carrier.
Magnetic materials have excellent stability and can catalyze organic reactions under harsh conditions (high temperature and high pressure). The catalyst supported by the magnetic nanoparticles is easy to be uniformly dispersed in a reaction system, thereby ensuring the catalytic activity; In most cases, magnetic materials as catalyst carriers are easy to recover and conducive to recycling. However, magnetic nanoparticles also have some shortcomings, such as easy to agglomerate and demagnetize, which affect their application range.

2.3 Other carrier load

In 2003, Fujihara et al. Adsorbed and loaded BINAP on the surface of metal nanoparticles with Au and Pd nanoparticles as carriers, respectively, to form BINAP-Au or BINAP-Pd nanocatalysts with optical activity[30]. In which Au and Pd nanoparticle are used as both active metal component and carriers. The asymmetric hydrosilylation of styrene over the catalyst was studied. When (S) -BINAP-Pd was used as the catalyst, (S) -1-phenylethanol was obtained by hydrosilylation and oxidation with a yield of 89% and an enantioselectivity of 75% ee. When the catalyst was (R) -BINAP-Pd, the enantioselectivity of (R) -1-phenylethanol was as high as 95% ee. The results showed that BINAP-Pd not only acted as a catalyst, but also acted as an inducer for the hydrosilylation of styrene.
The directly supported BINAP-M catalyst can be easily recovered and recycled in most cases, but the supported BINAP-M active center loses its mobility and reduces its degree of freedom, which will cause a series of problems such as mass transfer difficulties in the reaction process. Moreover, the intrinsic catalytic properties of BINAP-M will change with the change of its three-dimensional microenvironment. There is an erosion-catalysis-readsorption loading process in the catalytic reaction of supported catalysts, which will lead to the loss of active components of the catalyst and the uneven distribution of active components in the recovered catalyst, resulting in the decline of catalytic activity. In addition, in most supported catalysts, the active component only accounts for less than 1% of the total catalyst, and the carrier accounts for 99%. The sharp increase in the total mass of the catalyst will inevitably lead to the fact that the thermal conductivity and thermal capacity are determined by the carrier rather than the active component, which has a great impact on the activity of supported catalysts. The above limitations make the research results of directly supported catalysts have poor regularity, and even have the same carrier, active component and preparation method, but the catalytic effect is very different, and even the research conclusions are completely opposite.

3 Covalently supported BINAP-M catalyst

In order to avoid the disadvantages of adsorption-supported BINAP-M catalyst, such as easy loss of active components and low long-term recovery stability, the supported catalyst was prepared by covalent grafting of BINAP-M with the carrier to ensure the long-term stability of the catalyst and realize multiple recycling[31,32].

3.1 Mesoporous silica covalently supported

Mesoporous silica materials have excellent thermal and mechanical stability and pore size controllable structure. Moreover, the surface of mesoporous silica contains abundant silanol groups, which can covalently bond the catalytic active components to the surface of mesoporous silica, thus realizing the covalent loading of the catalytic active components, which is one of the most common types of covalently loaded catalysts[33].
SBA-15 is one of the most important ordered mesoporous materials, which is often used as catalyst support. Its ordered mesoporous structure provides a suitable place for the dispersion of substrates and products. In 2004, Lin et al. Synthesized a covalently supported catalyst which can be used to catalyze the hydrogenation of β-alkyl and β-keto acid ester compounds, that is, 4,4 '-functionalized BINAP and SBA-15 were covalently linked through saturated aliphatic hydrocarbons to obtain SBA-15 covalently supported BINAP-M catalyst[34]. They prepared two BINAP catalysts (8 a and 8 B, represented by SBA15-Ru(BINAP-L)(DMF)2Cl2, as shown in Scheme 8). The experimental results showed that the chiral selectivity of catalyst 8 a for the reduction of β-alkyl-β-keto esters to the corresponding β-hydroxy esters was up to 98. 6% ee.
In recent years, mesoporous silica nanospheres (MSNs), as a good catalyst support, can coordinate with the active component and play a dual-function catalytic effect. In 2009, Lin et al. modified the surface of MSNs with chiral (triethoxysilyl) propyl substituted ethylenediamine amino, and then coordinated with BINAP-Ru to obtain MSNs covalently supported catalyst MSNs-BINAP-Ru (9,10) (as shown in Figure 9)[35]. The average pore size and BJH surface area of the nanosphere catalyst were about 1. 8 nm and 1131 m2·g-1, respectively. The enantioselectivity of the obtained chiral phenethyl alcohol can reach up to 94% ee by using acetophenone derivatives as substrates. In the catalytic reduction of aromatic ketone substrates, the active component and the carrier are connected by siloxane through a flexible bridge chain, which slightly improves the enantioselectivity of the reaction product. The MSNs-48 catalyst with the highest catalytic activity was recycled and reused for 5 times, and the conversion and stereoselectivity of the catalyst still reached 99% and 68% ee, respectively. The carrier and the active component are covalently grafted through a long side chain, so that the supported catalyst has good space effect and can promote the improvement of the enantioselectivity of the catalyst. This loading strategy can be used in the design and preparation of more covalently supported catalysts, but the influence of the change of morphology and the generation of synergistic effect on the catalytic reaction mechanism needs further study and analysis.
Kumar et al. respectively functionalized the surfaces of two mesoporous silica materials MCM-41 and MCM-48, and then connected the carrier with BINAP and the metal complex in the form of a covalent bond through a "flexible bridge chain" to prepare a covalently supported BINAP catalyst on mesoporous silica (represented by Ru-SB-EN-MCM-41/48, as shown in Figure 10)[36]. Catalytic activity study show that that two catalysts show good catalytic activity and chiral selectivity for the catalytic hydrogenation of aliphatic ketone and aromatic ketones, the highest substrate conversion rate can reach 99%, and the highest stereoselectivity can reach 99% ee. The supported catalyst is used for the catalytic reduction of acenaphthene, the reaction conversion rate and the stereoselectivity can both reach more than 90%, and the catalyst shows excellent universal catalytic activity. In the catalytic reduction of 2-pentanone, the catalyst 11 was recovered by simple filtration and washing treatment, and reused for 4 times, the enantioselectivity and catalytic conversion still reached 93% ee and 93.3%. Under the same conditions, the stereoselectivity of catalyst 12 for the reduction of various ketones decreased significantly, for example, the selectivity for 2-pentanone was only 30% ee, which indicated that the diphosphine and diamine ligands coordinated with metal in the catalyst structure had a very important impact on the catalytic activity, while the supports MCM-41 and MCM-48 had a relatively low impact on the selectivity and conversion of the catalyst.
In 2008, van Koten et al. Bonded 5,5 '-diamino-BINAP-Ru/Rh complex with silica modified by aminopropyl silicon compound through ureido structure in the form of covalent bond to prepare covalently supported catalyst SiO2-BINAP-Ru/Rh(13) (as shown in Figure 11)[37]. The catalytic activity of catalyst 13 was evaluated by the reductive hydrogenation of the carbonyl group of asymmetric ketones or amides (such as β-ketoesters, acetamides, and acrylates) as a model reaction. The enantioselectivities of catalyst 13 were 99% ee and 85% ee, respectively, which were similar to those of homogeneous Ru-BINAP. Catalyst 13 was recovered by filtration and recycled five times with enantioselectivities above 99% ee.
In 2012, Crudden et al. Coupled the 5,5 '-position of BINAP with a siloxane compound through a covalent bond to obtain a siloxane precursor containing BINAP ligands, and hydrolyzed the precursor under acidic conditions to obtain an ordered mesoporous silica support embedded with BINAP ligands (represented by PMO-BINAP)[38]; Subsequently, the BINAP in the PMO-BINAP is coordinated with Ru to prepare a covalently supported BINAP catalyst having a special structure (represented by Ru-PMO-BINAP, as shown in Scheme 12). When the catalyst is used for the catalytic hydrogenation reaction of simple asymmetric ketone compounds, the catalyst shows excellent catalytic yield and ultrahigh enantioselectivity, both of which reach more than 99%. The catalyst and other components of the reaction system can be conveniently and quickly separated by centrifugal separation, and the activity of the catalyst is not obviously changed.
Although many covalently supported BINAP catalysts have been reported in recent years, they are mainly supported on silica, and most of them form covalent bonds bridged by carbon-heteroatoms. The carrier and covalent bond of these catalysts are relatively unstable to acid and alkali, and their application range is limited.

3.2 Polymer carrier load

In recent years, polymer materials as catalyst supports have attracted much attention. Homogenization in the reaction process of the supported catalyst can be realized by using the solubility of the polymer material in the organic solvent; At the same time, by using the solubility of the polymer carrier in different solvents, a new solvent can be added after the reaction to adjust the polarity of the reaction system, so that the catalyst is precipitated from the reaction system, and the separation of the catalyst from the reaction liquid mixture is realized[39⇓~41]. Polymer catalyst supports can be roughly divided into three categories: conventional polymer supports, dendritic polymer supports and mesoporous polymer supports.

3.2.1 Conventional polymer carrier

As the most common polymer carrier, polystyrene can be covalently grafted with BINAP through the flexible fatty chain. In 2001, Noyori et al. covalently grafted BINAP onto polystyrene through a long chain of N-methylvaleramide, and then performed a coordination reaction with [RuCl2(η6-benzene)]2 in DME as a solvent at 80 ° C to synthesize a RuCl2-BINAP heterogeneous catalyst covalently supported on polystyrene resin as a carrier (represented by PS-BIANP-Ru, as shown in Figure 13)[42]. The catalyst can effectively catalyze the hydrogenation reaction of various asymmetric aromatic ketone compounds and is convenient to recycle. For example, in the asymmetric hydrogenation of 1-acetonaphthalenone, the conversion and enantioselectivity of (R, RR) -15 a remained 100% and 98% ee after 7 reuses, and the TON value of (R, RR) -15 a still reached 3 3000 after 14 reuses. When the substrate was 2,4,4-trimethyl-2-cyclohexanone, the optimal conversion and enantioselectivity of (R, SS) -16 a were 100% and 94% ee, respectively, after 7 cycles. The TON value of (R, SS) -16 a can reach 27250. Compare with an unsupported BINAP-RuCl2, that catalyst has the same catalytic activity and enantioselectivity, and in comparison, the supported catalyst has bet recyclability, so that the catalyst has practical application value in the industrial production of the chiral secondary alcohol.
In 2017, Xu et al. prepared the Cu-PS- (S) -BINAP supported catalyst (as shown in Figure 14) by chloromethylation of polystyrene D101 as raw material, covalent bonding with 5,5 '-diamino-BINAP, and coordination with Cu[43]. The enantioselectivity of the catalyst Cu-PS- (S) -BINAP was discussed by studying the adsorption capacity of L-phenylalanine and D-phenylalanine. The adsorption equilibrium equation was established based on the concentration (C0 and Ce) and the volume V0 of D/L-phenylalanine solution before and after the adsorption equilibrium was reached, as well as the mass (W) of the catalyst 17 used. The adsorption capacity of D/L-phenylalanine was (qeL=57.34 mg/g,qeD=29.73 mg/g), and the enantioselectivity (α) was 1.93% ee. The catalyst 17 can be continuously recycled for 5 times in an acidic solution at pH = 1, and the enantioselectivity can be maintained at 2.7% ee.
The polymer carrier is directly connected with the chiral ligand through a simple covalent bond, so that the complexity of ligand modification can be reduced, the preparation process of the heterogeneous catalyst is simplified, and the consumption of raw materials for catalyst synthesis is reduced. However, compared with the polymer catalysts synthesized by copolymerization, the polymer catalysts directly covalently grafted can not control the distribution of the active sites of the catalyst well, which often leads to the reduction of enantioselectivity and the limitation of the catalytic system.
Itsuno's research group carried out the study of Ru-BINAP catalyst immobilized on Merrifield-type resin[44]. A series of 1,2-diphenyl-ethylenediamine (DPEN) modified cross-linked polystyrenes were synthesized by two routes (e.g., Scheme 15A and B), and then supported by Ru-BINAP and DPEN in polystyrenes to prepare BINAP-M catalysts (PS-BINAP-M-2) supported on Merrifield-type resins. The catalytic activity study showed that the conversion of acetophenone catalyzed by the catalyst was as high as 99%, and the enantioselectivity was more than 76% ee. The cross-linked polymer is insoluble in the reaction solvent, and the catalyst can be quickly separated and recovered by direct filtration, and the catalytic performance is not reduced after being recycled for 14 times.
In 2000, Lemaire et al introduced a methylamino group (represented by diam-BINAP) at the 6,6 '-position of the BINAP polymer monomer, and the monomer and 2-methyl-1,3-phenylene diisocyanate were subjected to polyaddition reaction to obtain an oligomer (S) -poly-BINAP (as shown in Scheme 16) with a degree of polymerization of 7 to 8, which was coordinated with a [RuCl2(benzene)]2 complex to prepare the (S) -poly-BINAP-Ru polymer catalyst[45]. The conversion of methyl acetoacetate was up to 100%, and the selectivity of R enantiomer of methyl 3-hydroxybutyrate was up to 99% ee when the loading of BINAP-Ru was 0. 1 mol%. The catalyst was recovered by filtration and reused 4 times, and the enantioselectivity of the catalyst still reached 99% ee.
With the deepening of research, Lemaire's team found that with the increase of the polymerization degree of 6,6 '-polyurea of BINAP (as shown in Figure 17), the rigidity of the polymer structure will increase, and the enantioselectivity of this supported catalyst for the asymmetric hydrogenation of methyl acetoacetate will also increase[46]. When the catalyst was recovered by filtration and reused three times, the catalytic conversion and enantioselectivity were still as high as 100% and 99% ee, respectively.

3.2.2 Dendrimer support

In 1994, Brunner and F Fürst reported eight kinds of diphosphine chiral small molecules with chiral substituents, which laid the foundation for the design of dendrimers[47]. In 1998, Brunner et al designed and prepared a chiral diphosphine Schiff base dendrimer with flexible aliphatic chain, which was coordinated with Ru complex and used to catalyze the asymmetric hydrogenation of (Z) -α-N-acetylalanine[48]. This class of chiral small molecules is considered to be the prototype of the first generation of dendritic chiral molecules designed with phosphine as the core. On this basis, a series of BINAP catalysts covalently supported on dendrimers were also studied.
In 2002, Fan et al. Successfully prepared a series of edge alkylated poly (arylene ether) ( "Fr Fréchet" type dendrimer) type dendrimer Ru-BINAP catalysts using 5,5 '-diamine-BINAP as the core and edge alkyl-functionalized polyether dendrimers through amide linkage (see schemes 18, 21 and 22)[49][50]. Using 2-phenylacrylic acid as the substrate and ethanol/n-hexane as the reaction solvent, the asymmetric hydrogenation of carbon-carbon double bonds was carried out, the conversion of the substrate was up to 100%, and the enantioselectivity of the catalyst 21-AB2-G2 was up to 90% ee. After the reaction, a small amount of water (2.5%) was added to the catalyst system, which could make the ethanol and n-hexane layered, and the catalyst entered the non-polar solvent n-hexane phase to achieve the separation effect, so the catalyst could enter the next catalytic cycle. After 4 cycles, the substrate conversion was still over 91% and the enantioselectivity was still up to 90% ee.
In 2004, Fan et al. Used 5,5 '-diamine-BINAP and dendritic dicarboxylic acid monomer as raw materials to prepare dendritic polymer with BINAP structure embedded in the molecule through polycondensation, and then coordinated with [Ru(benzene)Cl2]2 to prepare covalently supported dendritic polymer catalyst Ru-poly (BINAP) s of Ru-BINAP (as shown in Figure 19)[51]. Asymmetric hydrogenation of aryl ketones and 2-arylacrylic acids was carried out using the BINAP-Ru polymer catalysts dissolved in the reaction solvent. The BINAP-Ru polymer catalysts exhibited excellent enantioselectivities (73% -92% ee). The catalyst recycling performance was studied by using the reduction of dimethylacetophenone as a model reaction. The catalyst can be precipitated by adding methanol solvent to the reaction system after the reaction is finished, and can be directly reused after filtration and washing, and the enantioselectivity of the catalyst can still reach 91% ee after being recycled for three times.
In 2007, Fan et al designed and prepared a series of chiral dendrimer-supported BINAP catalysts (represented by GnDenBINAP-Ir, as shown in Figure 20) by covalently grafting carboxyl groups in specific dendrimers (Gn-COOH) with 5,5-diamino BINAP-Ir through amidation reaction[52]. The partial catalytic hydrogenation of 2-methylquinoline was used as a model reaction. When the catalyst dosage was as low as 1.1 mol%, the TOF value of 2-methyl-1, 2, 3, 4-tetrahydroquinoline was as high as 3450 h-1, the enantioselectivity was 93% ee, and the yield was more than 95% (TON ≈ 43000). The catalyst showed excellent recyclability Ir(G3DenBINAP). After the reaction, the catalyst was precipitated and filtered out by adding n-hexane solvent to the reaction system. After washing, the catalyst could be directly used. The enantioselectivity of catalyst 24 still reached 87% ee after six cycles. The solubility difference of dendrimer-supported BINAP catalyst in different solvents and the maintenance of high catalytic performance provide the possibility of its application in industrial production in the future.
In 2014, Fan et al. Synthesized a new chiral conjugated copolymer P-2 (as shown in Figure 21) with (S) -BINAP and fluorene as structural units. P-2 coordinated with [Ru(benzene)Cl2]2 to generate RuCl2-P-2, and then coordinated with dendrimer Gm-DPEN and [Ir(COD)Cl]2 respectively to construct chiral Ru/Ir bimetallic dendrimer catalysts 25a-c (as shown in Figure 21)[53]. The catalyst showed excellent activity and enantioselectivity in the asymmetric hydrogenation of 2-methylquinoline.The conversion of starting material reached 100% after 60 H, and the enantioselectivity of 2-methyl-1, 2, 3, 4-tetrahydroquinoline reached 73% ee. It is noteworthy that the reaction rate increases as the degree of polymerization of the dendrimer increases. This may be due to the specific structure of dendrimers which can effectively protect the catalytic active center iridium ion and prevent the dimerization of metal iridium, thus inhibiting the reduction of catalytic activity.
In 2009, Gade et al. Used hyperbranched polyethyleneimine (PEI) as a carrier and glutaric acid or carboxyl as a connecting unit to connect the PEI carrier with BINAP catalyst ligands through covalent bonds to prepare Carbo-BINAP and Glutaroyl-AMINAP polymer ligands, which were then coordinated with Cu to prepare Carbo-BINAP-Cu (26) and Glutaroyl-AMINAP-Cu (27) catalysts (as shown in Figure 22)[54]. Both catalysts showed excellent catalytic conversion and enantioselectivity for the hydrosilylation of acetophenone. The conversion and enantioselectivity of 26 catalyst with shorter chain length were 99% and 93% ee, respectively, after being reused for 3 times.

3.2.3 Porous polymer support

Porous polymer is a new type of polymer carrier, which has high specific surface area, large pore volume, high thermal and chemical stability. Porous polymers can also be easily modified to precisely graft catalytically active species into the porous polymer. As a catalyst support, it has been widely studied in carbon-carbon coupling reactions and chiral asymmetric catalysis.
In 2012, Xiao et al., using divinylbenzene and 5,5 '-diacrylamido BINAP as monomers, obtained a porous cross-linked chiral polymer (represented by PCP-BINAP) embedded with BINAP ligands by copolymerization, coordinated with Ru to prepare a PCP-BINAP-Ru catalyst (as shown in Figure 23), and studied the catalytic activity of the catalyst for the asymmetric hydrogenation of methyl acetoacetate[55]. When the ratio of catalyst PCP-BINAP-Ru to substrate was 1 ∶ 2000, the enantioselectivity of chiral methyl 3-hydroxybutyrate was 99% ee, and the catalytic conversion was 99. 5%. The reusability of the catalyst was evaluated with methyl methacrylate as the substrate, and the catalyst was directly recovered by filtration, and the catalytic conversion and enantioselectivity remained unchanged after 6 cycles.
In 2016, Ding et al. introduced unmodified BINAP into the polymer skeleton for the first time. They used benzene, biphenyl, 1,3,5-triphenylbenzene and BINAP as crosslinking units respectively, and obtained three different types of porous polymers (KAP-1, KAP-2, KAP-3) embedded in BINAP structure through simple Friedel-Crafts reaction and condensation of dimethanol formal, and then coordinated with [RuCl2(benzene)]2 to obtain the supported catalyst (as shown in Figure 24)[56]. The catalyst was applied to the hydrogenation of various β-keto esters with enantioselectivities (ee) over 94%. The method has the greatest advantage that the BINAP ligand can be directly used as a polymer monomer, and the dendrimer containing the BINAP structure can be obtained through Friedel-Crafts reaction polymerization, thereby forming an efficient, simple and recyclable polymer carrier heterogeneous catalyst.
Subsequently, Ding et al used (S) -4,4 '-divinyl BINAP and (S) -5,5' -divinyl BINAP as monomers to copolymerize with divinylbenzene (DVB), 1,3,5-tris (4-vinylphenyl) benzene and ethylene glycol dimethacrylate to obtain five types of porous organic polymers (represented by POP-BINAP) embedded with BINAP ligands, which were coordinated with Ru to prepare catalysts (30-34, as shown in Figure 25)[57,58].
The catalytic activities of the five catalysts for the asymmetric hydrogenation of methyl acetoacetate and the hydroformylation of styrene were investigated. When catalyst 30 was selected for hydrogenation, the enantioselectivity of chiral methyl 3-hydroxybutyrate was 94.3% ee, and the catalytic yield was more than 99.5%. Using methyl acetoacetate as the substrate, the catalyst 30 was recycled by filtration, and the catalytic yield of catalyst 30 could still reach more than 99. 5% and the enantioselectivity could reach more than 90% ee after six cycles. The regioselectivity of 2-phenylpropionaldehyde and the enantioselectivity of (R) -2-phenylpropionaldehyde were 8. 5% and 58. 9% ee, respectively, which were higher than those of the homogeneous catalyst (8. 1% and 35. 3% ee). After 7 cycles of the catalyst 32 by centrifugation and toluene washing, the enantioselectivity and regioselectivity still did not decrease significantly.
Although the structure, size, shape and solubility of polymers can be controlled by controlling the synthesis conditions, the regulation of polymer-supported BINAP catalysts can be realized, and the homogeneous catalytic reaction can also be partially realized. However, in most cases, the content of active component in the polymer-supported BINAP catalyst is low, and the steric hindrance of the support to the interaction between the reaction molecule and the active site is relatively large, so the activity of the polymer-supported BINAP catalyst is significantly reduced compared with that of the small molecule homogeneous catalyst. At the same time, if homogeneous catalysis is carried out, the catalyst needs to be precipitated after the reaction is completed, which inevitably increases new costs and product pollution. In addition, the poor stability of polymer supports in organic solvents at high temperatures and other conditions also limits their catalytic organic reactions.

3.3 Other carrier load

In 2003, Lin et al. carried out an in-situ sol-gel reaction between BINAP-Ru modified with 6,6 '-phosphoric acid and Zr(OtBu)4 to prepare a porous zirconium phosphate supported BINAP catalyst with Zr — O — P bond as a connecting unit (represented by Zr-Ru-BINAP-DMF, as shown in Figure 26)[59]. When the loading of active component BINAP-Ru-DMF was 1%, the enantioselectivity of Zr-Ru-BINAP-DMF could reach 95% ee when methyl acetoacetate was used as substrate. When the catalyst 35 was recycled five times, the enantioselectivity of the catalyst was still able to reach 88.5% ee.
In the same year, Lin et al. Further studied the porous zirconium phosphonate supported catalyst, replaced the ligand DMF with (S, S) -diphenylethylenediamine (DPEN), and prepared another chiral porous zirconium phosphonate catalyst Zr-Ru-BINAP-DPEN (as shown in Figure 27)[60]. The catalytic activity of Zr-Ru-BINAP-DPEN for acetophenone showed that the loading of active component was further decreased (loading was 0. 1%), while the enantioselectivity of Zr-Ru-BINAP-DPEN for acetophenone reached 99. 2% ee. The enantioselectivity was still as high as 99.0% ee when the catalyst was recycled 8 times.
Organometallic frameworks (MOFs) are a new class of porous molecular materials.Their structural characteristics of stability, easy separation, recyclability and adjustability make them excellent supports for heterogeneous catalysts. In 2014, Lin et al. First synthesized a chiral MOF catalyst with BINAP as the core[61]. With 4,4'-I2-BINAP as the starting material, the ligand 4,4 '-bis (methyl-4-carboxyphenylethynyl) -BINAP was prepared by Sonogashira coupling reaction, which was then coordinated with ZrCl4 to generate BINAP-MOF-Zr, which was then coordinated with Ru(COD)(2-Me-allyl)2 and [Rh(nbd)2](BF4)(nbd: dicycloheptadiene] respectively to successfully prepare catalysts Ru-BINAP-MOF-1 (37) and Rh-BINAP-MOF-2 (38) (as shown in Scheme 28). Methyl acetoacetate was prepared for catalysts 37 and 38 respectively. The enantioselectivity of methyl (R) -3-hydroxybutyrate could reach 97% ee when ethyl acetoacetate was used as substrate and catalyst 33 was used for catalytic hydrogenation under the pressure of 4 000 kPa. The enantioselectivity of (R) -3-phenylcyclohexan-1-one can reach 99% ee when the loading of Rh in catalyst 38 is 1 mol%. Catalysts 37 and 38 have a wide range of reaction adaptability, which creates the possibility for them to become potential industrial organic asymmetric catalysts.
Carbon-based materials have been regarded as one of the most important supports for supported catalysts due to their structural diversity, superior physical and chemical stability, and good compatibility with organic compounds. In 2012, Rodr Rodríguez-Ramos et al used graphene oxide (GO) as a carrier to prepare covalently supported catalysts Ru-DPEN-C-BINAP (39) and Ru-DPEN-I-BINAP (40) through the coordination reaction of chlorine-containing organosilane groups and chlorine-containing isocyanate groups with Ru-BINAP complex (as shown in Figure 29)[62]. Asymmetric hydrogenation of methyl acetoacetate was carried out. It should be noted that the catalytic efficiency of Ru-DPEN-I-BINAP was significantly lower than that of Ru-DPEN-C-BINAP, and the enantioselectivity was relatively low, only 45% ee. When the catalyst was recycled for the second time, 40 still maintained its original catalytic efficiency, while catalyst 39 lost its efficiency completely, indicating that the different connecting units between the support and the active component had an important impact on the loss of the active component and the stability of the catalyst.
In the study of covalently modified supported catalysts, controlling the appropriate space distance between the active site of the catalyst and the support can avoid their interaction, reduce the influence of the support, and maximize the retention of the original catalyst activity[63]. In this study, we tried to design and prepare graphene as a carrier, and covalently grafted the graphene carrier with BINAP-M through a flexible aliphatic "bridge chain" ”-(CH2)n- to obtain a graphene covalently supported catalyst G-(CH2)n-BINAP-M with a specific structure. From the analysis of the structural characteristics, the electron transfer between the carrier and the active site can not occur, and the "bridge chain" electron effect of straight chain fat is weak, which has little effect on the electron cloud density of BINAP naphthalene ring. At that same time, the appropriate 'bridge chain' chain length is selecte to reduce the steric hindrance of the graphene carrier to the active site of BINAP-M, thereby reduce the influence on the BINAP dihedral angle, maximally retaining the catalytic activity and stereoselectivity of BINAP-M, and also reducing the influence of mass transfer hindrance in the catalytic proces. Beside, that saturated fatty chain —(CH2)n— is use as a 'bridge chain' between a carrier and an active component, and compared with most catalysts use ester groups or amide groups as covalent 'bridge chains', the catalyst is more stable to acid and alkali media, so that the stability of the supported catalyst is improved. Therefore, the "straight chain flexible" structure of the G-(CH2)n-BINAP-M“ bridge chain ”—(CH2)n— enables the catalytic active site BINAP-M to have a high degree of freedom and effectively disperse into the reaction system to carry out "pseudo-homogeneous" reactions in the catalytic process. The special structure of GPh-(CH2)n-BM makes it have the advantages of both homogeneous catalysts and supported catalysts, which provides a new way for the study of catalysts.

4 Conclusion and prospect

To sum up, BINAP-M can be immobilized on various supports by simple adsorption and covalent bonding to prepare supported catalysts, which can solve the problems of catalyst active component recovery and reuse to a certain extent. How to design and prepare supported catalysts which are different from "classical" catalysts, and how to obtain high catalytic activity of homogeneous catalysts through structural control?The supported catalyst with high stability and convenient recovery and recycling is still a challenging work, which has important theoretical value and application significance in the field of catalyst design and preparation.

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Funding

National Natural Science Foundation of China(21971050)

Key Projects of Natural Science Research Projects in Colleges and Universities of Anhui Province(KJ2019A1248)

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