Polymeric Organocatalysts Research Articles

Bypassing halide immobilization with cooperative polymers for the cycloaddition of atmospheric CO2 to epoxides

Atom-economic syntheses of cyclic organic carbonates by cycloaddition of CO2 to epoxides have risen to prominence among various approaches for CO2 fixation. In current literature, there is a general lack of recyclable fully heterogeneous organocatalytic systems which are active under mild conditions (T≤60 °C, atmospheric pressure), and that do not involve elaborated synthetic steps for the synthesis of monomers or the coimmobilization of active sites such as hydrogen bond donors (HBDs) and halide nucleophiles. From the standpoint of cost reduction and sustainability, it is also highly desirable to obtain the catalytic materials from biobased sources, especially waste materials. To address such gaps in the literature, we disclose in this work that a lignin derivative (phenolated lignin, PL) can be used as HBD in cooperation with readily available ionic polymers to form recyclable heterogeneous catalytic systems able to carry out the target cycloaddition reaction under atmospheric pressure at 60 °C. This unprecedented approach allows the upcycling of readily available biobased materials for the mild synthesis of cyclic carbonates from CO2 and bypasses the need for elaborated synthetic procedures for the synthesis of coimmobilized HBD-halide systems. PL/QPBAE (quaternized polyaminoester) emerged among various PL/ionic polymer pairs as the most active and efficient catalyst. Such a result is justified through a spectroscopic and analytical investigation as an effect of the ability of PL and QPBAE to closely interact and disperse in the reaction medium, and of the higher flexibility of QPBAE compared to other ionic polymers such as quaternized polyvinylpyridine. The resulting catalytic pair can be used as an efficient recyclable system for the cycloaddition of CO2 to several epoxides under atmospheric conditions with a catalytic performance that compared very well to that of more complex oil-based state-of-the-art polymeric organocatalysts for the same reaction.

N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights

N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights

DFT Investigations on the Ring-Opening Polymerization of Trimethylene Carbonate Catalysed by Heterocyclic Nitrogen Bases

Organocatalysts for polymerization have known a huge interest over the last two decades. Among them, heterocyclic nitrogen bases are widely used to catalyse the ring-opening polymerization (ROP) of heterocycles such as cyclic carbonates. We have investigated the ring-opening polymerization of trimethylene carbonate (TMC) catalysed by DMAP (4-dimethylaminopyridine) and TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) as case studies in the presence of methanol as co-initiator by Density Functional Theory (DFT). A dual mechanism based on H-bond activation of the carbonyl moieties of the monomer and a basic activation of the alcohol co-initiator has been shown to occur more preferentially than a direct nucleophilic attack of the carbonate monomer by the heterocyclic nitrogen catalyst. The rate-determining step of the mechanism is the ring opening of the TMC molecule, which is slightly higher than the nucleophilic attack of the TMC carbonyl by the activated alcohol. The calculations also indicate TBD as a more efficient catalyst than DMAP. The higher energy barrier found for DMAP vs. TBD, 23.7 vs. 11.3 kcal·mol−1, is corroborated experimentally showing a higher reactivity for the latter.

SuFEx-Click Approach for the Synthesis of Soluble Polymer-Bound MacMillan Catalysts for the Asymmetric Diels–Alder Reaction

Novel polymeric MacMillan catalysts were prepared from modified chiral imidazolidin-4-one monomers via sulfur(VI) fluoride exchange chemistry. The resulting polysulfates containing chiral imidazolidin-4-one units could be employed as polymeric organocatalysts for the asymmetric Diels–Alder reaction. With the use of these polysulfate catalysts, sufficient catalytic activity and enantioselectivity were obtained, which were similar to those obtained by monomeric catalysts in a homogeneous catalytic reaction. In addition, the polysulfate catalysts could be recovered and reused five times without a considerable loss of activity and selectivity.

Secondary Sphere Effects on Porous Polymeric Organocatalysts for CO2 Transformations: Subtle Modifications Resulting in Superior Performance.

Albeit harnessing secondary sphere interactions to exert control over the reaction outcomes has primarily been applied to enzymatic and organometallic catalysis, there are seldom any studies that introduce outer-sphere modifiers into organocatalysts. This is even less in the corresponding heterogeneous catalytic system. In this contribution, we experimentally and computationally investigate the role of secondary effects in the reactivity of bromide anions toward CO2 transformations. Six pyridinium cationic porous frameworks have been synthesized and fully characterized. Structure-activity relationships and kinetics show that the type and the location of the substituents on the cationic framework have a significant impact on the nucleophilic reactivity of their bromide counter anion. Specifically, the attachment of amine substituent to the ortho position relative to a pyridinium motif produces a remarkably efficient catalyst for CO2 transformation, by a factor of six times greater in comparison to the pristine pyridinium-based polymer. The hydrogen-bond-interaction-promoted reagent activation and enhanced delocalization ability of bromide counter anion are believed to be the key to driving the reaction toward CO2 utilization. These observations, therefore, champion the leverage of secondary interaction for optimizing the reactivity of organocatalysts.

Synthesis of Cinchona Urea Polymers and Their Evaluation as Catalyst in the Asymmetric Reactions

AbstractChiral polyureas of cinchona alkaloids were synthesized via repetitive Mizoroki‐Heck (MH) coupling reaction. The Pd‐catalyzed polycondensation of cinchona urea dimers 6 and aromatic diiodide 7 afforded the chiral polyureas (P1−P4). The catalytic activity of the chiral polymers was subsequently investigated. The asymmetric Michael addition of ketoesters to nitroolefins was successfully catalyzed by the polymeric organocatalysts (P1−P4) to give the corresponding Michael adducts with high catalytic activities and excellent enantionselectivities (up to >99% ee). The polymeric catalysts were insoluble in commonly used organic solvents. They were easily recovered and reused several times without any loss of the catalytic activity.

ADMET Polymerization of Dimeric Cinchona Squaramides for the Preparation of a Highly Enantioselective Polymeric Organocatalyst

Under the acyclic diene metathesis (ADMET) reaction condition, the C3-vinyl groups of cinchona alkaloids readily react with each other to form a C-C bond. A novel type of cinchona alkaloid polymers was synthesized from dimeric cinchona squaramides using the Hoveyda-Grubbs’ second-generation catalysts (HG2) by means of ADMET reaction. The chiral polymers, containing cinchona squaramide moieties in their main chains, were subsequently employed as catalysts for the enantioselective Michael reaction to give the corresponding chiral adducts in high yields with excellent enantioselectivity and diastereoselectivity. Both enantiomers from the asymmetric Michael reaction were distinctively prepared while using the polymeric catalysts, possessing pseudoenantiomeric structures. The catalysts were readily recovered from the reaction mixture and recycled several times due to the insolubility of the cinchona-based squaramide polymers.

Bisurea and Bisthiourea H-Bonding Organocatalysts for Ring-Opening Polymerization: Cues for the Catalyst Design

A series of conformationally flexible bis(thio)urea H-bond donors plus base cocatalyst were applied to the ring-opening polymerization (ROP) of lactones. The rate of the ROP displays a strong depen...

Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones

Highly potent ionic organocatalyst is developed for room-temperature controlled ring-opening polymerization (ROP) of lactones, including δ-valerolactone, ε-caprolactone, and δ-hexalactone. The catalysts are prepared by simply mixing tetra-n-butyl ammonium hydroxide and a (thio)urea at elevated temperature under vacuum, and used in cooperation with an alcoholic initiator. The performance of the catalyst is readily adjusted and optimized through variation of the (thio)urea precursor, catalyst composition, and reaction condition. Urea-derived catalysts are generally superior to thiourea-derived ones. Provided with proper N-substituents, the catalyst affords both high polymerization efficiency and high selectivity for monomer enchainment over macromolecular transesterification, even at high monomer conversion and/or substantially extended reaction time. In addition to acidity, structural symmetry of the urea also proves decisive for the catalytic activity, which enables a catalyst-assisted proton transfer process for the ring-opening of lactone and thus provides a novel mechanistic insight for ROP catalyzed by hydrogen-bonding type bifunctional ionic organocatalysts.

Chitosan: A Natural and Sustainable Polymeric Organocatalyst for C-C Bond Formation During the Synthesis of 5-amino-2,3-dihydrobenzo[d] thiazole-4,6-dicarbonitriles

Background: A green, recyclable and reusable chitosan catalyst has been utilized for the synthesis of 5-amino-2,3-dihydrobenzo[d]thiazole-4,6-dicarbonitrile and its derivatives. Methods and Results: Three-component reaction protocol incorporates the reaction of aldehydes, malononitrile and rhodanine derivatives. This is examined as an efficient route for the synthesis of dicarbonitriles utilizing a green, biodegradable, environmentally benign, and easily available chitosan catalyst. In the reported protocol, catalyst can be recycled and not any substantial dropping in its catalytic activity during the recycling steps was obtained. Conclusion: A green and environmentally benign, one pot three-component protocol has been illustrated for the synthesis of 5-amino-2,3-dihydrobenzo[d]thiazole-4,6-dicarbonitrile derivatives. Adequately yield products were gained via the natural catalytic approach with the recyclability of the catalyst. The use of chitosan represents this procedure as an attractive substitute for the synthesis of biaryls complex by multicomponent reaction condition.

The mechanistic duality of (thio)urea organocatalysts for ring-opening polymerization.

Among the various catalysts for ROP, H-bonding organocatalysts stand out in the precise level of reaction control they are able to render during ROP. The H-bonding class of organocatalysts are thought to effect ROP via dual activation of both monomer and chain end. (Thio)urea mediated ROP has experienced a renaissance as a new polymerization mechanism - mediated by imidate or thioimidate species - facilitates new modes of reactivity and new synthetic abilities. Indeed, the urea class of H-bond donors has been shown to be more active than their corresponding thioureas. The imidate mechanism remains highly active in polar solvents and exhibits remarkable control - and 'living' behavior - under solvent-free conditions, and a broad range of temperatures is accessible. The advancements in synthetic abilities have all evolved through a greater understanding of reaction mechanism. Through the continued synergistic advances of catalysis and material, the (thio)urea class of catalyst can find use in a host of potential applications, research and industrial environments.

H-Bonding Organocatalysts for Ring-Opening Polymerization at Elevated Temperatures

The ring-opening polymerization (ROP) kinetics of e-caprolactone and lactide with various H-bonding organocatalysts, (thio)ureas paired with an amine cocatalyst, were evaluated at temperatures up to 110 °C. In nonpolar solvent, most cocatalyst systems exhibit decomposition at high temperatures, while only two, a monourea and bis-urea H-bond donor plus base cocatalyst, are stable up to 110 °C. The onset temperature of cocatalyst decomposition must be measured under reaction conditions. In polar solvent, when the more active imidate form of the (thio)urea is favored, most cocatalyst systems become thermally stable up to 110 °C, exhibiting linear Eyring behavior, including some that were unstable in toluene. The very progress of an ROP is shown to influence the nature of the catalysts as the solution polarity changes from highly polar (at 0% conversion) to less polar at full conversion. Activation parameters are discussed, and a mechanistic explanation of the observations is proposed.

Asymmetric Synthesis of Isoxazolidines on a Polymeric Organocatalyst

Key words prolinol - polystyrene - isooxazolidines - asymmetric catalysis - flow chemistry

Phosphazene Bases as Organocatalysts for Ring-Opening Polymerization of Cyclic Esters.

Over the past several years, organocatalyzed polymerization reactions have attracted considerable attention, and these efforts have led to major advances. A large number of organic compounds have been proven active for the polymerization of a large variety of monomers. In particular, phosphazene bases (PBs) are a family of extremely strong, non-nucleophilic, and uncharged auxiliary bases, and have shown their remarkable potential as organocatalysts for the ring-opening polymerization (ROP) of cyclic monomers. By deprotonation of weak acids or in combination with lithium cation, PBs significantly enhance the nucleophilicity of the initiator/chain-end, thus allowing fast and usually controlled anionic polymerization. In this feature article, the recent advances in phosphazene-catalyzed ROP of cyclic esters are summarized. This review is divided into three sections, including general features, design and synthesis, and catalytic applications. It aims to provide a critical analysis of PB-mediated ROP systems and a useful guide for the further design of organocatalysts applied to polymer synthesis. An outlook is given at the end.

A Pseudopeptide Polymer Micelle Used for Asymmetric Catalysis of the Aldol Reaction in Water.

Micelles assembled from amphiphilic molecules have proved to be ideal scaffolds to construct artificial catalysts mimicking enzymatic catalytic behavior. In this paper, we describe the synthesis of amphiphilic poly(2-oxazoline) derivatives with l-prolinamide units in the side chain and their application in asymmetric aldol reactions. Upon dissolution in water, the pseudopeptide polymers self-assembled into particles with different sizes, relying on the copolymer composition and distribution of hydrophilic/hydrophobic segments in the polymer chain. A preliminary study has demonstrated that the catalytic activity of these polymeric organocatalysts are strongly dependent on the aggregated architecture. The micelle-type assemblies can act as nanoreactors to efficiently promote the direct aldolisation of cyclohexanone with aromatic aldehydes in aqueous media, affording anti-aldol products in excellent yields (88–99%) and higher stereoselectivities (90/10 dr, 86% ee) compared to their nonmicellar systems under identical conditions.

Synthesis of chiral polyesters of cinchona alkaloid catalysts for enantioselective Michael addition of anthrone to nitroalkenes

Chiral polyesters of cinchona alkaloid derivatives were synthesized via repetitive Mizoroki-Heck (MH) coupling reaction. Under MH reaction conditions, 4-iodobenzoylquinine and 4-iodobenzoylcupreine were easily polymerized via self polycondensation to afford the corresponding chiral polyesters. The MH reaction conditions were also applied to the two-component polycondensation of cinchona ester dimer and aromatic diiodide to obtain the chiral polyesters. These cinchona-based chiral polyesters were successfully applied as polymeric organocatalysts in the asymmetric Michael addition reaction. The chiral polyesters bearing free OH groups at the C6′ position of the quinoline rings showed high catalytic activities (up to 97% isolated yield) and good enantioselectivities (up to 92% ee) in the Michael addition of anthrone to nitroalkenes. Furthermore, these polymeric catalysts were stable and could be recycled and reused several times.

Hydrogen Bonding-Based Non-Metallic Organocatalysts for Ring-Opening Polymerization of Lactones

Hydrogen Bonding-Based Non-Metallic Organocatalysts for Ring-Opening Polymerization of Lactones

Bifunctional Squaramides as Organocatalysts for Lactide Polymerization: Catalytic Performance and Comparison with Monofunctional Analogues

AbstractAmine‐functionalized squaramides 1 and 2 were prepared and shown to be suitable polymerization organocatalysts for the controlled ring‐opening polymerization (ROP) of l‐lactide (l‐LA) in the presence of an alcohol source such as BnOH (which acts as an initiator) to afford chain‐length‐controlled and narrow‐dispersion poly(l‐lactide) (PLLA) under mild reaction conditions. The ROP experimental and polymer analysis data are consistent with the action of 1 and 2 as bifunctional hydrogen‐bonding (HB) catalysts that are able to activate both the lactide monomer and initiator BnOH thanks to their dual HB acceptor and donor properties. As a comparison, aminosquaramide 3, a direct analogue of 1 but a weaker HB donor because of the absence of electron‐withdrawing NH substituents, displays little lactide ROP activity, which highlights the key role of monomer activation through HB in the present systems. Unlike aminosquaramides 1 and 2, related monofunctional squaramides 4 and 5 are inactive in l‐LA ROP in the presence of BnOH, but the addition of NEt3, as an external HB acceptor, allows the ROP to proceed with the production of well‐defined PLLA. A cooperative dual activation with an activated monomer/activated chain‐end mechanism is most likely operative in the lactide ROP mediated by 1 and 2 in the presence of BnOH.

Synthesis of cinchona alkaloid squaramide polymers as bifunctional chiral organocatalysts for the enantioselective michael addition of β-ketoesters to nitroolefins

Novel chiral polymers containing cinchona-based squaramides in their main chain structure were designed. We synthesized chiral squaramides bearing two cinchona moieties, which contain double bonds. Repeated Mizoroki-Heck reactions between the double bonds of the cinchona-based squaramide and aromatic diiodides proceeded smoothly to give cinchona squaramide chiral polymers. The catalytic activity of the chiral polymers was subsequently investigated. The asymmetric Michael addition of β-ketoesters to nitroolefins was successfully catalyzed by the polymeric organocatalysts to give the corresponding Michael adducts in good yields and excellent enantioselectivities of up to 99% ee. As the polymeric catalysts were insoluble in commonly used organic solvents, they were easily recovered from the reaction mixture and reused for further reaction without any loss of catalytic activity.

Mimicking enzymatic systems: modulation of the performance of polymeric organocatalysts by ion-specific effects.

Like natural enzymatic systems, our study has demonstrated that the activity of the polymeric organocatalysts can be modulated by ion-specific effects via the combination of anion-specific salting-in/out effects and anion-specific polarization of hydrogen bonding induced stabilization of the transition state.