Donor Catalysts Research Articles

Carbon-Bromide Bond Activation by Bidentate Halogen, Chalcogen, Pnicogen, and Tetrel Bonds.

Halogen, chalcogen, pnictogen, and tetrel bonds in organocatalysis have gained noticeable attention. In this work, carbon-bromide bond activation in the Ritter reaction by bidentate imidazole-type halogen, chalcogen, pnicogen, and tetrel bond donors was studied by density functional theory. All of the above four kinds of catalysts exhibited excellent catalytic performance. σ-hole interactions were formed between the Br atom of the reactant and the halogen, chalcogen, pnicogen, and tetrel bond donors, which elongated the C-Br bond and caused the rearrangement of the electron density of the precomplexes, resulting in the breaking of the C-Br bond and Br abstraction. Notably, the catalytic activity of the chalcogen bond is the best, followed by that of the halogen bond. Although the catalytic activity of pnicogen and tetrel bond catalysts is not as good as that of the halogen bond and chalcogen bond, they can still be used as effective substitutes for the halogen bond and chalcogen bond, providing more choices for noncovalent catalysis. Furthermore, within the same group, the fifth-period atomic catalyst is more effective than the fourth-period one for halogen, chalcogen, pnicogen, and tetrel bond donor catalysts.

Intramolecular Silanoxy-Michael Reactions with Pendant Nitroalkenes: Racemic and Enantioselective.

We present the first racemic and scalemic examples of di-tert-butyl silanoxy-Michael additions. Our operationally simple protocol is selective for nitro-olefins and simply involves stirring the substrate with an appropriate hydrogen-bond donor catalyst without any special precautions to exclude air or moisture. For each substrate examined, we have developed complementary protocols that optimize yield and enantioselectivity. Our reactions scale well, and the products are valuable intermediates for further transformations, including for the preparation of enantioenriched vicinal amino alcohols.

A cobalt templated outer sphere hydrogen bond donor catalyst derived from 2-guanidinobenzimidazole: Synthesis, applications in carbon–carbon bond forming reactions, structure

A lipophilic tricationic cobalt tris(chelate) complex of 2-guanidinobenzimidazole (GBI), [Co(GBI)3]3+ 3BArf– (23+ 3BArf–; BArf = B(3,5-C6H3(CF3)2)4), is prepared from the corresponding hydrophilic trichloride salt and Na+ BArf– or Ag+ BArf– under aqueous/organic biphasic conditions. This racemic chiral complex, which is obtained as a mer isomer and a tetradecahydrate as assayed by NMR and TGA, is an excellent catalyst for additions of dimethyl malonate and indole to trans-ß-nitrostyrenes (10 mol%), and cycloadditions of CO2 to epoxides (1 mol%; solvent-free). Average yields (84 %, 91 %, 81 %) and rates are slightly greater than those obtained with a monocationic ruthenium GBI complex [(η5-C5H5)Ru(CO)(GBI)]+ BArf– prepared earlier. Attempted crystallization of 23+ 3Cl– gives a tetramethanol solvate of a salt derived from loss of two molecules of HCl. This can be represented as [Co(GBI)(GBI–H)2]+ Cl−, and bond lengths and hydrogen bonding motifs are carefully analyzed, especially in the context of dominant chelate resonance forms.

A Type of Chiral C2-Symmetric Arylthiol Catalyst for Highly Enantioselective Anti-Markovnikov Hydroamination.

The development of chiral hydrogen donor catalysts is fundamental in the expansion and innovation of asymmetric organocatalyzed reactions via an enantioselective hydrogen atom transfer (HAT) process. Herein, an unprecedented type of chiral C2-symmetric arylthiol catalysts derived from readily available enantiomeric lactate ester was developed. With these catalysts, an asymmetric anti-Markovnikov alkene hydroamination-cyclization reaction was established, affording a variety of pharmaceutically interesting 3-substituted piperidines with moderate to high enantioselectivity. Results of the designed control experiments and theoretical computation rationalized the origin of stereocontrol and disclosed the spatial effect of the moiety of chiral thiols on the enantioselectivity. We believed the facile synthesis, flexible tunability, and effective enantioselectivity-controlling capability of these catalysts would shed light on the development of versatile chiral HAT catalysts and related asymmetric reactions.

Development of Silica‐Immobilized Material as Heterogeneous Hydrogen Bond Donor (HBD) Catalyst: Synthesis of Cyclic Carbonates from CO2 and Epoxides

AbstractComposite silica materials have been developed by hydrothermal method and utilized as heterogeneous Hydrogen Bond Donor (HBD) catalysts, where the functionalized ketimine derivatives have been immobilized on the solid support. Such functional materials have been found to be efficient catalysts for the synthesis of cyclic carbonates through the installation of CO2 with epoxides. Characterization of these materials was systematically done using various spectroscopic and imaging techniques to confirm the presence of organic compounds on the silica surface. These composite materials exhibited significantly higher catalytic activity as compared to the other homogeneous methods. Additionally, this synthetic process was extremely convenient in terms of all the external parameters such as, solvent free condition at ambient reaction temperature with normal pressure of CO2, very low catalyst loading with proper regeneration and reusability of the catalyst. These facets have definitely made this technique greener and more sustainable.

Unconventional sulfonium C–H H-bond donor catalyst in fixation of carbon dioxide

Sulfonium featuring multiple α-C–H was revealed as a new type of H-bond donor catalyst in the cycloaddition of CO2 to epoxides.

Halogen bond catalysis of the [4+2] cycloaddition reaction of 2-alkenylindoles: catalytic modes and stereoselectivity.

Halogen bond donor catalysts have been widely used in organic reactions because they are environmentally friendly, inexpensive and recyclable. The [4+2] cycloaddition reaction is a key reaction in organic synthesis because of its ease of use, fast speed, and wide range of applications. In this work, halogen bond catalysis in the [4+2] cycloaddition reaction between 2-alkenylindoles was investigated based on DFT calculations. There are two modes of I⋯π halogen bond catalysis: either on the ethenyl of 2-alkenylindole (mode A) or on the five-membered ring of 2-alkenylindole (mode B). Both modes involve two steps: the formation of carbon-carbon bonds and the formation of six-membered rings. Gibbs free energy barriers were determined to investigate the stereoselectivity of the endo pathway and exo pathway. For mode A, the exo products were more easily generated when the substituent R = H, and the N-H⋯π interaction promoted high endo selectivity in the case of the substituent R = Ph. For mode B, an increasing proportion of endo products can be obtained in the order of catalyst I2, IBr and ICl. The π⋯π interaction of the substituent R = Ph promotes the [4+2] cycloaddition reaction, which is consistent with the experimental observation that R = Ph has a higher yield than R = H. The study of different catalytic modes and stereoselectivity would provide new ideas for the further study of the [4+2] cycloaddition reaction.

Halide-free pyridinium base binary organocatalyst for the cycloaddition of carbon dioxide to epoxides

An organocatalyst composed of a common organic base and hydroxypyridine is a new type of H-bond donor catalyst efficient in the cycloaddition of CO2 to epoxides.

Asymmetric Dearomatization of Phthalazines by Anion-Binding Catalysis.

A straightforward methodology for the enantioselective synthesis of 1,2-dihydrophthalazines via dearomatization of phthalazines by anion-binding catalysis has been developed. The process involves the Mannich-type addition of silyl ketene acetals to in situ generated N-acylphthalazinium chlorides using a tert-leucine derived thiourea as a H-bond donor catalyst. Ensuing selective and high-yielding transformations provide appealing dihydro- and tetrahydro-phthalazines, phthalazones, and piperazic acid homologues, en route to biologically relevant molecules.

Metal-organic framework boosts heterogeneous electron donor–acceptor catalysis

Metal-organic framework (MOF) is a class of porous materials providing an excellent platform for engineering heterogeneous catalysis. We herein report the design of MOF Zr-PZDB consisting of Zr6-clusters and PZDB (PZDB = 4,4’-(phenazine-5,10-diyl)dibenzoate) linkers, which served as the heterogeneous donor catalyst for enhanced electron donor–acceptor (EDA) photoactivation. The high local concentration of dihydrophenazine active centers in Zr-PZDB can promote the EDA interaction, therefore resulting in superior catalytic performance over homogeneous counterparts. The crowded environment of Zr-PZDB can protect the dihydrophenazine active center from being attacked by radical species. Zr-PZDB efficiently catalyzes the Minisci-type reaction of N-heterocycles with a series of C-H coupling partners, including ethers, alcohols, non-activated alkanes, amides, and aldehydes. Zr-PZDB also enables the coupling reaction of aryl sulfonium salts with heterocycles. The catalytic activity of Zr-PZDB extends to late-stage functionalization of bioactive and drug molecules, including Nikethamide, Admiral, and Myristyl Nicotinate. Systematical spectroscopy study and analysis support the EDA interaction between Zr-PZDB and pyridinium salt or aryl sulfonium salt, respectively. Photoactivation of the MOF-based EDA adduct triggers an intra-complex single electron transfer from donor to acceptor, giving open-shell radical species for cross-coupling reactions. This research represents the first example of MOF-enabled heterogeneous EDA photoactivation.

Development of Suitable Hydrogen Bond Donor (HBD) Catalysts for the Synthesis of Cyclic Carbonates and Dithiocarbonates from Epoxide

Development of Suitable Hydrogen Bond Donor (HBD) Catalysts for the Synthesis of Cyclic Carbonates and Dithiocarbonates from Epoxide

Sustainable Organocatalytic Processes to Access Alkyl SuFEx Click Hubs and Tetrasubstituted Carbon Centers: Potential Libraries for Multidisciplinary Applications

AbstractIn this Account, we provide an overview of our recent achievements on sustainable organocatalysis. Our group has unveiled the effectiveness of specific organocatalysts under various environmentally benign conditions. We have found that N-heterocyclic carbene and phosphazene superbases exhibit favorable performances in bulk aqueous reaction environments. In addition, the use of organic superacid catalysts results in synergistic effects when hydrogen-bond donor catalysts are assembled in aqueous media. Moreover, we discovered that a neutral organic salt precatalyst can generate a potent silylium Lewis acid catalyst in situ, specifically under solvent-free conditions. These innovative, sustainable organocatalytic processes have successfully facilitated the conversion of raw starting materials into valuable compounds, including sulfur(VI) fluoride exchange (SuFEx) click hubs and tetrasubstituted carbon centers incorporating heteroatoms.1 Introduction2 Water-Accelerated N-Heterocyclic Carbene (NHC) Catalysis for β-Aminosulfonyl Fluorides3 Water-Accelerated Phosphazene Superbase Catalysis for β-Sulfidosulfonyl Fluorides and γ-Geminal Dithioester-Incorporated Sulfonyl Fluorides4 Water-Accelerated Synergistic Superacid Catalysis for α-Tertiary Amines5 Solvent-, Metal-, and Purification-Free PPM (parts per million) Neutral Organic Salt Catalysis for Tertiary Cyanohydrin Derivatives6 Conclusion

Direct π‐Activation vs. O‐Activation in Halogen‐Bonding Catalysis

AbstractHalogen bond donors had an increasing impact on catalysis in recent years, and their development is highly active. In particular, numerous iodine‐based halogen bond donors have been developed and used to promote various reactions through coordinating carbonyl groups, a ubiquitous mode of activation in catalysis. We now report computational data which strongly suggests that an alternative activation mode, through direct π‐complexation, is operative for unsaturated carbonyl substrates. Calculations also suggest that solvent polarity could have a clear impact on the preference of the mode of activation, raising the possibility of a mechanistic manifold switch through solvent variation. These findings could profoundly impact the development of the next generation of halogen‐bond donor catalysts.

Direct π-Activation vs. O-Activation in Halogen-Bonding Catalysis.

Halogen bond donors had an increasing impact on catalysis in recent years, and their development is highly active. In particular, numerous iodine-based halogen bond donors have been developed and used to promote various reactions through coordinating carbonyl groups, a ubiquitous mode of activation in catalysis. We now report computational data which strongly suggests that an alternative activation mode, through direct π-complexation, is operative for unsaturated carbonyl substrates. Calculations also suggest that solvent polarity could have a clear impact on the preference of the mode of activation, raising the possibility of a mechanistic manifold switch through solvent variation. These findings could profoundly impact the development of the next generation of halogen-bond donor catalysts.

In Situ Synergistic Catalysis Hydrothermal Liquefaction of Spirulina by CuO-CeO2 and Ni-Co to Improve Bio-oil Production.

Hydrothermal liquefaction (HTL) is one of the most promising technologies for biofuel production. The preparation and application of catalysts for HTL have been the research focus in recent years. In this study, a new synergistic catalytic process strategy is proposed. CuO-CeO2/γ-Al2O3 was used as an in situ hydrogen donor catalyst and Ni-Co/SAPO-34 was synthesized for hydroprocessing to improve bio-oil production process. The results of XRD and XPS demonstrated that the metal components were well supported on the catalyst. When the two catalysts were mixed, the yield of bio-oil increased from 51.00% to 64.51%, the carbon recovery rate raised from 69.53% to 88.18%, the energy recovery rate grew from 63.42% to 80.22%, and the S content is relatively reduced by 83.3%. Also, TG analysis showed that the content of light components in bio-oil increased. Moreover, the hydrocarbons and alcohols were observed to a higher proportion from the GC-MS analysis. This new method still has high catalytic activity after repeated use for five times. This study provides a new idea for preparing higher yield and superior quality bio-oil.

Post-Modification of Octahedral Chiral-at-Metal Cobalt(III) Complexes by Suzuki–Miyaura Cross-Coupling and Evaluation of Their Catalytic Activity

A family of well-defined Λ- and Δ-configured octahedral cationic chiral-at-cobalt catalysts were expanded through a straightforward postcomplexation of the bromine-functionalized Co(III) complexes based on (R,R)-1,2-cyclohexanediamine and (S,S)-1,2-diphenylethylenediamine by Suzuki–Miyaura cross-coupling reaction (CCR) with arylboronic acids. The corresponding modified Co(III) complexes were isolated by standard silica column chromatography with up to 65% yields. Indeed, it is the first example of the direct modification of the ligand sphere of chiral Co(III) catalysts through Suzuki–Miyaura CCR. It was observed for the first time that the chiral metal center is epimerized during the cross-coupling process at the transmetalation stage on palladium catalyst in the case of minor diastereomers of Co(III) complexes (Δ(R,R)-1 and Λ(S,S)-2). Next, the efficacies of obtained chiral metal-templated complexes 1–4 were evaluated in benchmark asymmetric reactions in order to compare their catalytic activity. Chiral Co(III) complexes 1–4 have been examined as hydrogen bond donor (HBD) catalysts in such important reactions as epoxidation of chalcone and the fixation of CO2 into valuable cyclic carbonates.

Insight of polypropylene synthesis with high performance multidentate internal donor catalyst system

AbstractPropylene polymerization using magnesium dichloride (MgCl2) supported Ziegler–Natta (Z–N) system is a robust and preferred catalytic process for producing polypropylene (PP) grades. Herein, synthesis of polypropylene products is reported using MgCl2 supported multidentate (3,3,3′,3′‐tetramethyl‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobiindane‐5,5′,6,6′‐tetracarbonate) Z–N pre‐catalyst. The catalyst performance evaluation over propylene polymerization found that multidentate Z–N pre‐catalyst has better hydrogen response with controlled isotacticity of PP products as compared to conventional bidentate Z–N pre‐catalysts. Melt rheology analysis showed higher loss modulus and storage modulus for ultra‐high molecular weight isotactic polypropylene (UHMWiPP) as compared to PP resins with medium molecular weight. Further, GPC analysis reveal medium to broad unimodal molecular weight distribution (MWD) of PP products produced with multidentate Z–N pre‐catalyst system.

Iodine(I)-based and iodine(III)-based halogen bond catalysis on the Friedel-Crafts reaction: a theoretical study.

Halogen bond catalysis, especially iodine derivatives catalysis, has attracted increasing attention in recent years owing to the advantages of relatively cheap, stable, green, easy to handle, and favorable catalytic activity. To obtain insights into the catalytic mechanism and activity of halogen bond donor catalysts, iodine(I)-based and iodine(III)-based halogen bond catalysis on the Friedel-Crafts reaction were investigated in this study. The entire reaction contains several key steps: carbon-carbon bond coupling, proton transfer, hydroxyl departure, indole addition, and deprotonation process. According to the energetic span model, iodine(III)-based donor catalysts exhibit higher catalytic activity than iodine(I)-based catalysts and double cationic catalysts are more potent than single cationic ones. For halogen bond catalysis, the Gibbs energy barriers have linear relation to the electron density at the halogen bond critical points. Furthermore, the Gibbs energy barriers are also linearly related to the integral charge values of the increased region of electron density outside the oxygen atom of reactants. Therefore, the stronger halogen bond results in lower Gibbs energy barrier, and the stronger polarization further benefits the halogen bond catalysis.

Exploring Structure-Function Relationships of Aryl Pyrrolidine-Based Hydrogen-Bond Donors in Asymmetric Catalysis Using Data-Driven Techniques.

Hydrogen bond-based organocatalysts rely on networks of attractive noncovalent interactions (NCIs) to impart enantioselectivity. As a specific example, aryl pyrrolidine substituted urea, thiourea, and squaramide organocatalysts function cooperatively through hydrogen bonding and difficult-to-predict NCIs as a function of the reaction partners. To uncover the synergistic effect of the structural components of this catalyst class, we applied data science tools to study various model reactions using a derivatized, aryl pyrrolidine-based, hydrogen-bond donor (HBD) catalyst library. Through a combination of experimentally collected data and data mined from previous reports, statistical models were constructed, illuminating the general features necessary for high enantioselectivity. A distinct dependence on the identity of the electrophilic reaction partner and HBD catalyst is observed, suggesting that a general interaction is conserved throughout the reactions analyzed. The resulting models also demonstrate predictive capability by the successful improvement of a previously reported reaction using out-of-sample reaction components. Overall, this study highlights the power of data science in exploring mechanistic hypotheses in asymmetric HBD catalysis and provides a prediction platform applicable in future reaction optimization.

Dibenziodolium Salts as Halogen Bond Donor Catalysts for the Reduction of Quinolines, One‐Pot Reductive Amination, and Addition Reaction with Indoles

AbstractThe efficiency of dibenziodolium salts as halogen bond donor catalysts was investigated by studying various organic transformations. Diverse reactions were carried out with low catalytic loading and under mild conditions. The catalyst was found to be efficient for carrying out the reduction of quinolines, one‐pot reductive amination, Michael addition reaction of indoles with chalcones, and Friedel‐Crafts reaction of indoles with isatin with a low catalytic loading of 3 mol %. A wide substrate scope was attempted for all the transformations. Several control experiments were carried to rule out the possibility of hidden Brønsted acid catalysis. NMR studies and preliminary DFT calculations suggest the presence of halogen bond between the catalyst and the substrate.