Abstract
The recent advances on green and sustainable organocatalysis are revised in this chapter. An important focus on one of the 12 principles of green chemistry, organocatalysis pursues to reduce energy consumption as well as to optimize the use of different resources, targeting to become a sustainable strategy in organic chemical transformations. In last decades, several experimental methodologies have been performed to make organocatalysis an even greener and sustainable alternative to stoichiometric approaches as well as non-catalytic conditions by the use of benign and friendlier reaction media. In this line, several approaches using water as preferential solvent, alternative solvents such as ionic liquids including chiral ones, deep eutectic solvents, polyethylene glycol (PEG), supercritical fluids and organic carbonates or solvent-free methodologies have been reported. In this chapter, we mainly focus on the recent remarkable advancements in organocatalysis using green and sustainable protocols.
Keywords
- water
- solvent-free
- heterogeneous organocatalysis
- alternative solvents
- sustainable organocatalysis
1. Introduction
Aqueous reactions can combine the unique physical properties exhibited by water and other desirable advantages from the point of view of environmental concerns, safety and low cost. For many cases, the application of water is limited due to the reduced solubility and stability of diverse organic substrates in aqueous media as well as the problems associated with possible contamination of water phase with organic substrates and the need of efficient purification steps. Alternatively, the strategy to use solvent-free organocatalysed reactions has also been explored. In these cases, a large excess of reagent, which acts as reaction media avoiding the additional use of auxiliary solvents is tested. Alternative solvents such as ionic liquids (ILs); acyclic and cyclic carbonate and polycarbonate solvents (e.g. dimethylcarbonate and polyethylenoglycol derivatives); fluorinated solvents and supercritical carbon dioxide have been largely explored for catalytic processes. In this context, the large number of examples is centred in the application of ionic liquids including chiral ones as efficient reaction media for several organic transformations. Taking advantage of physical, chemical and thermal properties of ionic liquids as well as the possibility to tune their properties according to the adequate cation-anion combinations, it is possible to develop designer solvents for organocatalytic reactions. Also, the high capacities to solubilize and stabilize different organic, inorganic and polymeric materials as well as the reusable and recyclable behaviour are relevant parameters to justify the large application of ionic liquids in synthesis and catalysis. Recent advances showed the potential use of supercritical carbon dioxide as unique solvent or in combination with ionic liquids for efficient reaction-extraction processes. Supported catalytic processes as efficient, greener and recyclable methodologies for some organocatalytic processes have been also described. The organocatalysts including chiral ones can be incorporated in solid supports improving their stability and catalytic activity as well as the possibility to reuse and recycle several times without significant decrease in their performance. The use of alternative techniques such as microwave irradiation and ultra-sons (sonication) instead of the traditional synthetic protocols will be also reviewed. One of the most important challenges of synthetic chemistry is related with the combination of efficiency, reduced costs and environmental impact in the production of relevant molecules, particularly for the preparation of chiral compounds. The creation of chiral centres can be achieved by several methodologies such as by using chiral auxiliaries, readily obtained by chemical manipulation of chiral natural and non-natural compounds by asymmetric catalysis including biocatalysis.
2. Organocatalytic reactions in water
Traditionally, the majority of organic reactions have been performed in organic solvents, mainly due to the fact that most organic compounds are not very water-soluble. In addition, many reagents used in organic synthesis are destroyed by water. This fact is contradictory to what happens in nature, where reactions promoted by enzymes and antibodies take place in aqueous media. Despite their utility in solubilising substrates and reagents, organic solvents are toxic and volatile. Water has a few obvious advantages over organic solvents [1–4]; it is relatively abundant, non-toxic, non-flammable and inexpensive. In addition, it has a large temperature window in which it remains in the liquid state and high heat capacity, making it a good and safe heat sink for exothermic reactions, particularly important when they are carried out on a large scale. Water also has a large dielectric constant, high surface tension, hydrogen bonding capacity and optimum oxygen solubility. Since the solvent is usually present in large excess, it can play an important role in the reaction. Initially, it was thought that the presence of water was only detrimental to organic reactions [5]; it brought insolubility problems, and it could react with functional groups from different substrates, slowing them down and causing low yields. Due to its capacity to form hydrogen bonds, water could disrupt H-bonding in transition states, i.e. those formed between catalyst and substrate molecules, deteriorating catalytic activity and stereocontrol. Pioneering studies by Breslow showed that Diels-Alder reactions were accelerated in water [6]. This fact was a surprise, since Diels-Alder reactions are relatively insensitive to solvent polarity. He determined that the acceleration was due to the fact that in the presence of water, the less polar reagents would be drawn together in hydrophobic hydration, resulting in a more favourable overall entropy. The increase in concentration led to rate enhancements. In 2005, Sharpless showed that many uni- and bimolecular reactions were accelerated when carried out in vigorously stirred aqueous media [7]. Reactions which took place as an emulsion displaying rate acceleration, he described as taking place ‘on water’. It would later be observed that under the right conditions the benefits of water may be not only to rate acceleration but also to increased selectivity (vide infra). The effect of water on organocatalytic reactions was investigated even when the first examples of this type of catalysis were studied, i.e. in the direct proline-catalysed aldol reaction (Scheme 1). This reaction, in which two unmodified carbonyl compounds react to give a β-hydroxy carbonyl product, is used by aldolase enzymes for the biosynthesis of carbohydrates, keto acids and some amino acids. In organic synthesis, the organocatalytic direct aldol version is catalysed by chiral amines via
2.1. The direct aldol reaction
The capability of proline (1) to promote asymmetric direct intra-molecular aldol reactions was shown in the Hajos-Parrish-Eder-Sauer-Wiechert cyclisation in 1971. However, despite the utility of this reaction for the synthesis of steroids, it would be only 30 years later that the broad applicability of this catalyst would be discovered and the first inter-molecular version of the direct aldol was described by List and Barbas [11]. High yields and stereoselectivities can be obtained with proline catalysis in organic solvents, but addition of water to the reaction mixture lowers the yields and stereoselectivities, not only in these examples but also in other studies reported in subsequent years. In the asymmetric direct aldol reaction, the chemo-, regio-, diastereo- and enantioselectivity should be controlled. Side reactions are possible, which reduce the yield: aldol condensation, aldol reaction and condensation of the aldehyde acceptor and also oxazolidinone formation between the catalyst and the aldehyde. Excess ketone is often used to prevent aldehyde homodimerisation and catalyst kill events. Another inherent problem is that aldol reactions are very difficult to achieve under stoichiometric conditions, since the equilibrium constants for many direct ketone-aldehyde aldol reactions are just barely on the side of the products. Pihko and co-workers were the first to observe significant rate enhancements, yield and stereoselectivity increases in the proline-catalysed aldol reaction when small amounts of water (1–10 equiv.) were added to a DMF solution of acetone or 4-thianone and various aromatic aldehydes [12]. The effect obtained was such that the reaction could be performed with equimolar quantities of reagents. The beneficial role of water was attributed to a suppression of the competing reaction which leads to oxazolidinone formation. The first direct aldol reactions performed solely in water were later described independently by Hayashi [13] and Barbas [14] in 2006. To achieve their aim, these authors developed novel organocatalysts derived from proline containing hydrophobic groups. In these reactions, aldehyde and ketone substrate molecules aggregate excluding water, thus generating a two-phase system. Hayashi’s catalyst, 4-siloxyproline 2 (Scheme 1) operates in the organic phase where enamine formation takes place. A reaction in this heterogeneous system was defined by Hayashi as a ‘
In an emulsion, hydrophobic catalysts also reduce the contacts between the transition state and bulky water. Catalysts 2 and 3 were less efficient in reactions with non-activated aldehydes showing lower yields and
The concepts applied in the development of catalysts 2–4 would also be used for catalyst design in subsequent years (Scheme 1). Proline analogues obtained through derivatisation of the carboxyl or the amino groups and 4-hydroxyproline derivatives have predominated. These reactions are usually
Due to space limitations, in the examples the highlighted solvent was usually pure water without the addition of any organic co-solvents, although in some cases one of the carbonyl components was used in excess and could play the role of a solvent too.
Gryko studied in more detail hydrophobic aggregation processes [16]. The use of different salting-in and salting-out conditions in the reaction between cyclic ketones and aromatic aldehydes catalysed by protonated thioamide 5 showed that both the reaction rate and stereochemistry were affected by the rate of hydrophobic aggregation. Around this time, Singh described a very efficient prolinamide (6) for
In 2008, Gong developed highly reactive prolinamide 9, showing that only 1 mol% was enough to catalyse the direct aldol between a wide range of aromatic aldehydes and 2 equiv. of cyclic or linear ketones in water to afford products in high yields and
Despite all these developments, during the next five years the organocatalytic direct aldol reaction still continued to attract considerable attention and catalysts with novel backbones were reported. Luo used primary-tertiary diamine Brønsted acid 15 to obtain the otherwise difficult to get
In an early study on the cross-aldol reaction of ketones catalysed by proline, Garden and co-workers explored the effect of water [28]. They found that when excess acetone was reacted neat with isatins, which may be viewed as a type of activated ketones, addition of small amounts of water gave large enhancements in yields and
2.2. The Mannich reaction
The asymmetric Mannich reaction is one of the most important methods for the synthesis of enantioenriched molecules containing a stereogenic carbon-nitrogen bond. Of lately, there have been several reports on Mannich reactions performed in organic solvents to which small amounts of water were added [1, 37]. Reported methods using water as unique reaction media are few, probably because this is more difficult to achieve due to the inherent susceptibility of the imine substrates to hydrolysis [1]. Enamine catalysis was used in all cases. The first reaction performed solely in water was described by Ibrahim and Córdova in 2006 [38]. They showed that 10 mol% of TMS-protected prolinol
In 2007, a three-component Mannich reaction of O-benzyl hydroxyacetone,
2.3. The Diels-Alder reaction
The Diels-Alder reaction was one of the first organocatalytic asymmetric reactions to be studied in pure water [46]. In 2002, Northrup and MacMillan reported that linear and cyclic enones reacted with cyclopentadiene in the presence of the chiral amine salt of oxazolidinone 26, to give bicyclic adducts in good yields and high stereoselectivities (Scheme 2) [47]. The reaction presumably proceeds via the formation of an intermediate iminium, a process which lowers the energy of the HOMO, facilitating the cycloaddition. When
The reaction promoted by 28 was initially developed as a one-pot procedure involving addition of aldehydes to nitroolefins, followed by
3. Organocatalytic reaction in alternative solvents
In previous years, the search of alternative solvents as sustainable reaction media for asymmetric organocatalysis have been reported [54]. In particular, ionic liquids including chiral ones: polyethylene glycol (PEG) derivatives, organic carbonates and supercritical fluids are the major examples of alternative solvents already tested with comparable or even better performances than conventional organic solvents [55].
3.1. Ionic liquids and chiral ionic liquids
Ionic liquids as organic salts with low melting point (lower than 100°C) have emerged as environmentally benign alternative media to classic organic solvents [56]. Some peculiar properties of ILs such as their almost negligible vapour pressure, high thermal stability, high ionic conductivity, large electrochemical window, insolubility in supercritical CO2 (
The possibility to use different ILs as efficient and recyclable reaction media is one important parameter for applications in organocatalysis. Additionally, the organocatalyst can be dissolved and stabilized into IL allowing to preserve its catalytic activity for several cycles [57]. In 2002, two independent reports [58, 59] showed the possibility to use ILs as alternative solvent for asymmetric aldol reaction between acetone and some aromatic aldehydes in the presence of (S)-proline (1–30 mol%) as organocatalyst. The best results (94% yield and 89%
Chiral ionic liquids (CILs) have been recognized as having potential application for chiral discrimination, including in asymmetric synthesis and resolution of racemates [69]. A transfer of chirality in these solvents should be expected; however, only a few number of chiral ILs have been reported to date [70]. The initial report from Seddon and co-workers [71] showed the preparation of CIL [bmim][Lactate] for application in catalysis. Then, a number of new chiral ILs have been synthesized and employed as chiral additives in order to induce moderate enantioselectivity in some reactions such as in Aldol reaction, photo-isomerisation, the Baylis-Hillman reaction and Michael additions [72]. Recently, several chiral ILs have been reported based on introduction of chiral units in the organic cation or anion by efficient synthetic methods. In parallel, many examples have described the use of natural chiral sources such as aminoacids or commercially available chiral compounds such as chiral carboxylic or sulphonic acids [73]. A larger number of reported chiral ionic liquids derive their chirality from the cationic moiety. Taking advantage of the readily available chiral precursors such as amines, aminoalcohols and amino acids, it is possible to incorporate them in cationic structures.
In this context, Bica and co-workers [74] reported the synthesis and application of basic chiral ILs based on (S)-proline incorporating alkylpyrrolidinium cations and NTf2 as anions. The authors designed these CILs in order to replace trifluoroacetic acid in enamine-based organocatalysis for asymmetric C-C bond reactions. In the case of asymmetric aldol reaction of 4-nitrobenzaldehyde and acetone, moderate to high yields and enantioselectivites (up to 80%
3.2. Polyethylene glycol and deep eutectic solvents (DESs)
Polyethylene glycol as alternative media for asymmetric aldol reaction was first reported in 2004 by the Chandrasekar group [80]. The authors tested different aldehydes and ketones with comparable yields and enantioselectivities than conventional organic solvents. Also, PEG400 and Proline as catalyst were recycled at least 10 times without any decrease in the activity. In 2011, Verma et al. [81] described PEG-embedded thiourea dioxide (PEG.TUD) as an useful and recyclable host-guest complex organocatalyst for the synthesis of 3, 4-dihydropyrimidones via Biginelli condensation in order to afford the desired pure product in high yields. It is interesting to know that these results are in contrary to unreactive PEG-thiourea complexes (PEG.TU) for similar reaction condition processes. Despite the potential use of PEG derivatives as biocompatible alternative reaction media for organocatalysis, only few examples in the literature have been reported.
Deep eutectic solvents were first introduced by Abbott and co-workers [82] to describe the formation of a liquid eutectic mixture (mp 12°C) starting from two solid materials with high melting points: choline chloride (ChCl, mp 133°C) and urea (mp 302°C) in a molar ratio of 1:2. DES are generally formed by suitable combinations of two or three safe and inexpensive components which are able to engage in hydrogen-bond interactions with each other to form an eutectic mixture with a melting point lower than either of the individual components. The application of DES as alternative solvent for catalysis is very promising mainly because no purification is required; their physicochemical properties can be easily tuned according to specific reaction requirements, and they offer convenient methods of product isolation simply based on organic phase extraction or even precipitation upon addition of water, which can be subsequently removed, thereby restoring a reusable DES [83]. In recent years, DES have been applied in the fields of biotransformations, metal-catalysed reactions, organometallic chemistry and also in organocatalysis. Benaglia and co-workers [84] published three distinct stereoselective reactions (addition reactions: isobutyraldehyde to β-nitrostyrene; E-3-methyl-3-nitroethylacrylate to benzylacetone and 4-hydroxycoumarin to benzaldehyde) catalysed by a chiral primary amine through different activation methods. For these reactions, they tested three different DES (choline chloride: urea, 1:2; choline chloride: fructose; water, 1:1:1; choline chloride: glycerol, 1:2) in order to obtain the desired chiral products in high yields and enantioselectivities. Also, the use of these unconventional and biorenewable reaction media based on DES allowed the recovery and the recycling of the chiral catalyst.
3.3. Supercritical fluids and organic carbonates
The use of supercritical carbon dioxide (
Organic carbonates have been claimed as alternative low cost and biodegradable solvents for application in organocatalytic reactions [88]. North et al. [89] reported ethylene and propylene carbonate as an alternative solvent in asymmetric aldol reactions catalysed by (S)-proline. Using cyclic and acyclic ketones reacting with aromatic aldehydes, the desired chiral aldol products were obtained in good yields and high stereoselectivities. Additionally, an appropriate combination between propylene carbonate and the proline enantiomer was observed allowing a considerable improvement in the stereoselectivity of aldol product [90]. The same authors also reported the use of cyclic carbonates as solvents for α-hydrazination of aldehydes and ketones by diazodicarboxylates using (S)-proline as organocatalyst [91].
4. Organocatalytic reaction under solvent-free conditions
On the road to sustainability, organic chemistry has been changing and the application of catalytic processes has contributed to a more efficient use of energy, less waste and the exploration of raw materials [92]. Indeed, sustainability is a growing concern in the twenty-first century, and consequently the use of solvent-free reactions in organic chemistry is gaining importance, with a foremost impact in the environmental protection as well as on human health. Organic reactions in the absence of conventional organic solvents have become highly attractive. Consequently, over the last years, the number of reactions under solvent-free conditions has grown.
4.1. Aldol reactions
The solvent-free enantioselective organocatalysed reactions have been reviewed [93] and this chapter focuses on the most recent advances. Kumar and co-workers have recently reported two new prolinamide catalysts 32 and 33 for direct stereoselective organocatalytic and direct aldol reaction of aldehydes and ketones to produce the corresponding β-hydroxy carbonyl compounds under neat conditions [94, 95]. Catalyst based on myrtanyl-prolinamide that was synthesized in two steps from
Additionally, the same group has further used solvent-free conditions and evaluated the use of three (
4.2. Michael addition reactions
Asymmetric organocatalysed reactions under solvent-free conditions have been extended to Michael addition reactions. Recently, Bolm and co-workers developed an efficient, solvent-free protocol for Michael addition reactions of α-nitrocyclohexanone to nitroalkenes using thiourea derivatives as catalysts [101]. These reactions have been carried out in sustainable conditions, using planetary ball mill, with low catalyst loading and short reaction times, leading to high yields (up to 97%) and high enantioselectivities (
The organocatalytic Michael reaction of ketones with γ-monohalonitrodienes was reported by the Xu group using chiral prolinethiol ether as organocatalyst for the synthesis of functionalized monohaloalkenes, under solvent-free conditions [106]. After optimisation of the reaction conditions, the reaction scope was examined and several substitutions on the aromatic ring were investigated (for X = Br), and several groups were well tolerated (e.g.
4.3. Mannich reaction
Organocatalysed Mannich reactions have also been recently explored under solvent-free conditions. Fioravanti and co-workers have reported the synthesis of trifluoromethyl
5. Organocatalytic reaction using heterogeneous systems
The immobilisation of homogeneous organocatalysts using several supports has been quite explored in previous years since in general their heterogenisation allows more stable and efficient catalyst. These parameters are aligned to the demands of sustainability and economical scalability issues. Several supports have been used: mesoporous silica [112, 113], biopolymers as chitosan [114, 115], synthetic polymers as polystyrene and polyacrylamide [116], carbon nitrides [117], metal organic frameworks (MOFs) [118], dendrimers [119], graphene [120] and magnetic nanoparticles [121–123].
5.1. Recent approaches in heterogeneous organocatalysts
Corma and Garcia have reported silica-bound organocatalysts as heterogeneous, recoverable and recyclable catalysts in several organic transformations [112]. Heterogeneous organocatalysts based on organically modified hybrid mesoporous silica (mainly MCM-41 and SBA-15) and their efficiency in several organic transformations have been also reviewed by Rostamnia [113]. These types of supports are very stable, biocompatible and can be functionalized with a wide range of functional groups. In general, their resultant-supported organocatalyst is more stereoselective, chemoselective and efficient than the homogeneous analogous. The organic moieties supported include: amines (primary, secondary and tertiary), sulphonic acids, acid-based bi-functionalized systems, ephedrine, proline, urea, thiourea and guanidine and fluorinated alcohol [114]. Kadib [114] and Mahé et al. [115] summarized the field of organocatalytic reactions promoted by chitosan used as an insoluble organocatalyst or as a support for organocatalysts. Chitosan is ranked as the second most abundant polysaccharide after cellulose and it is obtained from deacetylation of chitin, which is exclusively extracted from industrial marine discharge. Chitin is constituted by
In the previous years, dendrimers have also attracted the attention of the scientific community as they combine the advantages of homogeneous catalysts, showing fast kinetic behaviour, and heterogeneous catalaysts, since they can be easily separated from the reaction mixture by precipitation, membrane or nanofiltration methods. Wang et al. described the recent advances for metallodendritic catalysts and dendritic organocatalysts [119]. Magnetic nanoparticles are another interesting supports for heterogenisation of organocatalysts since it allows their recovery with sustainable techniques of magnetic separation. Magnetite, also known as ferrite (Fe3O4), has a very active surface suitable for functionalisation or adsorption of several metal- and organic-based catalysts. In general, these heterogeneous catalysts are highly stable and can operate under mild conditions, using environmentally benign solvents or even water, with good performances and recyclabilities [121–123]. They have been applied in a wide range of reactions, such as Mannich-type reactions, C-C, C-S and C-O coupling reactions, alkylation, oxidation, reductions and asymmetric synthesis. Mrówczyński et al. summarized their use as supports for organocatalysts [122], their use in asymmetric catalysis has been reviewed by Dalpozzo [123] and their application in catalysis, green chemistry and pharmaceuticals reactions are described by Gawande et al. [121]. Bartók reports the advancements of heterogeneous asymmetric direct aldol reactions using organocatalysts based on hydroxyproline, prolinamide and peptides immobilized by covalent or ionic bonding and by adsorption on different supports [124]. In order to allow the application of organocatalysts in industry, their scale-up using continuous flow technology has attracted much attention in recent years. Three very interested reviews in this field were published recently [125–127]. Puglisi et al. [126] and Atodiresei et al. [127] reported several types of asymmetric organocatalysed reactions in continuous flow and highlighted their advantages over batch reactors. Heterogeneous-supported organocatalysts are focused on both reviews. This field is still in its infancy since the examples known are applicable mostly for particular substrates and with some problems of catalyst deactivation. However, in general these processes improve the efficiency of the organic transformations by reducing the amount of catalyst loading and reactions times. Very recently, Munirathinam et al. [125] reviewed the main achievements that has been in this area but focusing on a broader range of supported catalysts including acid, base, organomettalic, peptidic, enzymatic, ionic liquids and metal nanoparticles by using the three main approaches to incorporate them into the catalytic micro-reactors: (i) packed-bed, (ii) monolithic and (iii) inner wall-functionalized. The application of these catalytic micro-reactors on several reactions and their advantages over classical batch reactors were also presented.
5.2. Some examples of heterogeneous organocatalysts in solvent-free conditions
SBA-15 mesoporous silica functionalized with mercaptopropyl groups were used for the covalent immobilisation of multi-layered ionic-liquid-like phases containing imidazolium or thiazolium active sites [128]. These new hybrid materials were used for the etherification of 1-phenylethanol under solvent-free conditions at 160°C under different gas phase (oxygen, air, nitrogen and argon). The best catalytic performances were obtained for the material bearing thiazolium groups under oxygen, and this hybrid material also showed higher catalytic activity (92% of conversion and 75% of selectivity, under O2, 160°C, 7 h) when compared with its homogeneous analogous catalyst (92% of conversion and 72% of selectivity in the same reaction conditions). For example, the heterogeneous catalyst was recycled seven times, without loss of activity, for the etherification of 1-phenylethanol. Other two alcohols were also tested: benzyl alcohol and diphenylmethanol. García-Suárez et al. [129] have tested for the first time the catalytic activity of a Bio-IL [Chol][Pro] (choline-proline) in the Michael addition reaction and supported this catalyst on different heat-treated mesoporous carbon materials by simple physical adsorption in organic media, reporting also the catalytic activity of the heterogeneous systems. The coupling of cyclohexanone and β-nitrostyrene to produce 2-(2-nitro-1-phenylethyl)cyclohexanone was selected to evaluate the catalytic activity of the catalysts, under solvent-free and at room temperature conditions. Excellent conversions and high diasteroselectivities were obtained for the heterogeneous catalysts based on commercially available mesoporous carbon beads heated at 1500°C and 2000°C. These results are similar to those obtained for the homogeneous catalyst. The stability of the supported Bio-IL is strongly influenced by the textural and surface chemical properties of the supports tested.
Recently, the group of Wang [130] described a new method for the hollow-structured phenylene-bridged periodic mesoporous organosilica (PMO) spheres using hematite (α-Fe2O3) nanoparticles as a hard template. These materials were functionalized with MacMillan catalyst (H-PhPMO-Mac) by a co-condensation process and a ‘click chemistry’ post-modification and by grafting. For comparison, analogous materials were prepared in the absence of hematite. Their catalytic activity was tested in asymmetric Diels-Alder reaction using water as solvent. The model reaction tested was the Diels-Alder cycloaddition of 1,3-cyclopentadiene with trans-cinnamaldehyde. The catalyst H-PhPMO-Mac has shown higher catalytic activity (98% yield, 81% enantiomeric excess (
The same group reported for the first time the incorporation of 4-(
A new approach to obtain chiral metal organic frameworks as heterogeneous asymmetric photocatalysts through the cooperative combination of stereoselective organocatalyst L-or D-pyrrolidin-2-ylimidazole (PYI) and a triphenylamine photoredox group into a single framework was developed by Duan, He and co-authors [135]. Two enantiomeric MOFs of Zn were prepared and applied to prompt the light-driven α-alkylation of aliphatic aldehydes with high catalytic efficiency and enantioselectivity. For comparison, lanthanide-based MOFsHo-TCA (H3TCA = 4, 4´,4´´- tricarboxyltrihexylamine and MOF-150, assembled from 4,4′,4″-nitrilotribenzoic acid, were studied and the results suggested that both photosensitizer triphenylamine and the chiral organocatalyst were necessary for the light-driven reaction. However, the corresponding MOF obtained by mixing the chiral moiety has shown lower enantioselectivity. Two chiral porous MOFs functionalized with carboxylic acid groups were reported for the first time by Liu et al. [136]. One of them was able to encapsulate S)-2-(dimethylaminomethyl) pyrrolidine by combining the carboxylic acids and chiral amines
6. Organocatalytic reactions using sustainable synthetic protocols
Over the past two decades, many efforts have been made both in industry and academia to develop synthetic organic protocols using more efficient methodologies with the aim to protect the environment and prevent waste. With that goal in mind, sustainable mechanochemical processes such as high-speed ball [138–140] microwave (MW) [138, 141, 142] or ultrasound [143] are being increasingly used in the synthetic organic chemistry [144]. Employing this unconventional energy inputs, it is conceivable to offer innovative and highly appropriate alternatives to traditional synthetic processes [145, 146]. The use of microwave or ultrasound in organocatalytic processes have been previously reviewed by others [147, 148].
MW irradiation offers several advantages over conventional heating, such as instantaneous and rapid heating (deep-inside heating), high temperature homogeneity and selective heating [138, 142, 148, 149]. The observed enhancement of the reaction rate is in part associated with the rapid heating caused by MW irradiation relative to the same reaction using conventional heating. Beyond the controversial debate around the existence or not of non-thermal microwave effects, we must have to accept that MW chemistry is an effective, safe, rapid and highly reproducible way to perform chemical reactions that recently were translated to continuous flow processes [149, 150]. Also, the possibility to performing the MW and ultrasound reactions in the absence of a solvent is a major advantage [151]. An example is the Michael addiction of diethyl malonate to several enones catalysed by (
Recently, the same authors describe an efficient three-component domino [3+1+1] heterocyclisation to 2-(2´-aza-aryl)imidazoles promoted by K2CO3 under microwave irradiation conditions [157]. This one-pot operation makes use of mild conditions and short reaction times of 20–32 min and excellent atom economy. An interesting mechanism involving a umpolung process has been proposed for the formation of the 2-(2’aza-aryl)imidazoles [157]. Catalytic amounts (10 mol%) of bis-arylureas and bis-thioureas promote the Friedel-Crafts alkylation between nitroolefins and aromatic and heteroaromatic N-containing derivatives [158]. Best results are noticed on running the reactions in the absence of solvent. When applied to indoles, this protocol provides the corresponding Michael adducts in good to excellent yields and with high selectivity.
Chiral tetrahydroisoquinoline-based guanidines were prepared by Naicker and collaborators [168] using a microwave-assisted synthesis. The prepared catalyst was applied as chiral catalysts to promote the asymmetric 1,4-addition of β-keto esters or malonates to nitroolefins in up to 97%
The aldol reaction is one of the most important carbon-carbon bond formation reactions widely employed in synthetic organic chemistry. Proline has also an important role as organocatalyst on this reaction. Liao and co-workers [170] developed a microwave-based procedure to promoted direct aldol condensation using polystyrene-supported amine catalyst. Microwave greatly shorten the reaction times to only 20 min and improved the yield significantly. This procedure has the advantage of recovering the catalyst by simple filtration and can be reused for at least four times without significant loss of reactivity. The synthesis of heterocycles can be achieved under mild conditions using microwave irradiation. Gangwar et al. [171] using oxalic acid as catalyst reported the preparation of 3,4-dihydropyrimidin-2(1H)-one derivatives by Biginelli reaction between aromatic aldehydes, ethylacetoacetate or methylacetoacetate and urea under microwave irradiation for 2–5 min. The oxalic acid was used in very low quantity (2 mol%). The antioxidant properties were evaluated and the compounds having −OH group on benzene ring were found to have higher activity. A new, efficient and convenient approach to the synthesis of new extended angular fused aza-heterocycles including dibenzacridine and naphth[2,3-a:2',3'-j] acridine units with good luminescent properties is described [172]. The multicomponent reactions (MCRs) were conducted by reacting readily available and inexpensive starting materials using thiosalicylic acid as a catalyst under microwave irradiation. A total of 14 examples were examined, and a broad substrate scope and high overall yields (72–89%) were revealed. 1,2,3-Triazoles are an interesting class of heterocyclic unit widely used in the discovery and modulation of drug candidates. The copper-free cycloaddition reaction of azidophenyl arylselenides with β-keto-esters under catalysis of diethylamine and microwave irradiation allowed the synthesis of high-functionalized-1,2,3-triazole in good to excellent yield. With microwave irradiation it was possible to reduce the reaction time from hours to few minutes [173]. The proposed mechanism involves [3 + 2] cycloaddition reaction between the azide group and the enamine followed by elimination of the diethylamine catalyst. A very interesting MW-assisted formation of polysubstituted salicylaldehydes from propargyl vinyl ethers using imidazole as catalyst was developed by Tejedor et al. [174]. A diverse array of salicylaldehydes from simple aromatic monocyclic to complex fused polycyclic systems was obtained in moderate to high yields (38–72%). Using this procedure, it was possible to achieve the benzophenone-derived natural product morintrifolin B in a five-step synthesis. The authors proved that the reaction is scalable and instrumentally simple to perform, highly regioselective and takes place under symmetry-breaking conditions. Symmetrically substituted propargyl vinyl ethers afforded asymmetrically substituted salicylaldehydes. Some protocols are being developed for the microwave-assisted catalytic Wittig reaction. Recently, Hoffmann, Werner and Deshmukh [175–177] address this subject and a very extensive study was carried out to find the scope and limitations of this reaction. Among the several catalysts tested, epoxides proved to be suitable masked bases for this reaction. Phosphine oxides Bu3P = O proved to be the most promising catalyst that can be reduced
In another approach, McNulty and collaborators [178] have shown that it is possible to achieve high (
Warfarin is one of the most effective anticoagulants used as a racemate. However, the (S)-form proved to be more active to its mirror image [183]. Warfarin can be achieved by the asymmetric Michael addition catalysed by organic primary amines and under ultrasound. The conjugate addition of the enolate from the 4-hydroycoumarin to an α,β-unsaturated ketone, with catalysis of (
Acknowledgments
This work was supported by LAQV-REQUIMTE and Fundação para a Ciência e a Tecnologia through projects (PEst-C/LA0006/2013) one contract under Principal Investigator FCT (L.C. Branco) and post-doctoral grant (SFRH/BPD/111168/2015).
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