Special Issue "Organocatalysis: Advances, Opportunity, and Challenges"

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: 31 October 2021.

Special Issue Editors

Prof. Dr. Tatiana G. Chulkova
E-Mail Website
Guest Editor
Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg, 199034, Russia
Interests: physical organic chemistry; reaction mechanisms; catalysis in organic chemistry
Dr. Evgeny Bulatov
E-Mail Website
Guest Editor
University of Jyväskylä, Department of Chemistry, Nanoscience Center, Survontie 9 C, 40500 Jyväskylä, Finland
Interests: organic synthesis; coordination and organometallic chemistry; catalysis; chemically active materials for 3d-printing; optical spectroscopy; crystallography

Special Issue Information

Dear Colleagues,

Catalysis with small organic molecules has become a highly dynamic area in chemical research. Today, organocatalyzed reactions provide an alternative to metal-catalyzed reactions in creating of a wide range of organic compounds in a convenient manner. The advantages of organocatalysis include the use of inexpensive and readily available organic compounds as catalysts, as well as increased synthetic efficiency, as no metal catalyst needs to be removed at the end of the process. These benefits could lead to the application of such processes in the industry. A relatively new concept is the use of chiral organic catalysts. In this area, new opportunities are opening up for the development of extremely active catalysts that rival the efficiency of enzymes and that of the few superactive chiral transition metal complexes, such as Noyori’s hydrogenation catalysts or certain cross-coupling reaction catalysts.

Submissions to this Special Issue on “Organic Chemistry in Catalysis” are welcome in the form of original research papers or short reviews that reflect the state of research in the field of organocatalysis on the following topics: selective organocatalytic reactions, asymmetric organocatalysts, element–organic compounds in organocatalytic reactions, noncovalent interactions in organocatalysis, and the study of the mechanisms of organocatalytic reactions.

Prof. Dr. Tatiana G. Chulkova
Dr. Evgeny Bulatov
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • organocatalytic reactions
  • asymmetric organocatalysis
  • reaction mechanisms
  • noncovalent interactions
  • element–organic compounds as organocatalysts

Published Papers (8 papers)

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Research

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Article
Flow-Through Macroporous Polymer Monoliths Containing Artificial Catalytic Centers Mimicking Chymotrypsin Active Site
Catalysts 2020, 10(12), 1395; https://doi.org/10.3390/catal10121395 - 30 Nov 2020
Cited by 2 | Viewed by 477
Abstract
Synthetic catalysts that could compete with enzymes in term of the catalytic efficiency but surpass them in stability have a great potential for the practical application. In this work, we have developed a novel kind of organic catalysts based on flow-through macroporous polymer [...] Read more.
Synthetic catalysts that could compete with enzymes in term of the catalytic efficiency but surpass them in stability have a great potential for the practical application. In this work, we have developed a novel kind of organic catalysts based on flow-through macroporous polymer monoliths containing catalytic centers that mimic the catalytic site of natural enzyme chymotrypsin. It is known that chymotrypsin catalytic center consists of L-serine, L-histidine, and L-aspartic acid and has specificity to C-terminal residues of hydrophobic amino acids (L-phenylalanine, L-tyrosine, and L-tryptophan). In this paper, we have prepared the macroporous polymer monoliths bearing grafted polymer layer on their surface. The last one was synthesized via copolymerization of N-methacryloyl-L-serine, N-methacryloyl-L-histidine, and N-methacryloyl-L-aspartic acid. The spatial orientation of amino acids in the polymer layer, generated on the surface of monolithic framework, was achieved by coordinating amino acid-polymerizable derivatives with cobalt (II) ions without substrate-mimicking template and with its use. The conditions for the preparation of mimic materials were optimized to achieve a mechanically stable system. Catalytic properties of the developed systems were evaluated towards the hydrolysis of ester bond in a low molecular substrate and compared to the results of using chymotrypsin immobilized on the surface of a similar monolithic framework. The effect of flow rate increase and temperature elevation on the hydrolysis efficiency were evaluated for both mimic monolith and column with immobilized enzyme. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Communication
Organocatalyzed Michael Addition to Nitroalkenes via Masked Acetaldehyde
Catalysts 2020, 10(11), 1296; https://doi.org/10.3390/catal10111296 - 09 Nov 2020
Cited by 1 | Viewed by 1024
Abstract
A novel and safe reaction protocol for the enantioselective enamine-catalysed addition of acetaldehyde to nitroalkenes is presented; this protocol makes use of a safe acetaldehyde precursor to access important intermediates to Active Pharmaceutical Ingredients (APIs), and allows the use of fewer equivalents of [...] Read more.
A novel and safe reaction protocol for the enantioselective enamine-catalysed addition of acetaldehyde to nitroalkenes is presented; this protocol makes use of a safe acetaldehyde precursor to access important intermediates to Active Pharmaceutical Ingredients (APIs), and allows the use of fewer equivalents of acetaldehyde and lower catalyst loadings. The reaction developed proved to be suitable to be performed on gram-scale and to produce key intermediates for the synthesis of pharmacologically active compounds such as pregabalin. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Article
Baeyer-Villiger-Including Domino Two-Step Oxidations of β-O-Substituted Primary Alcohols: Reflection of the Migratory Aptitudes of O-Substituted Alkyl Group in the Outcome of the Reaction
Catalysts 2020, 10(11), 1275; https://doi.org/10.3390/catal10111275 - 03 Nov 2020
Viewed by 461
Abstract
Following the recent development of the one-pot two-step oxidation protocol for primary β-alkoxy alcohols, additional primary β-oxy alcohols were examined under similar conditions. The outcome of these reactions closely follows the migratory aptitudes of the related α-oxy-alkyls in Baeyer-Villiger oxidation vs. that of [...] Read more.
Following the recent development of the one-pot two-step oxidation protocol for primary β-alkoxy alcohols, additional primary β-oxy alcohols were examined under similar conditions. The outcome of these reactions closely follows the migratory aptitudes of the related α-oxy-alkyls in Baeyer-Villiger oxidation vs. that of hydrogen. Thus, these experiments helped to establish the correct order of these aptitudes for α-oxy-alkyls. Furthermore, in the case of primary β,β-dialkoxyalcohols, the formation of dialkoxymethyl formates by the domino oxidation reaction was followed by secondary reactions, forming a number of interesting products. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Article
Double Spirocyclization of Arylidene-Δ2-Pyrrolin-4-Ones with 3-Isothiocyanato Oxindoles
Catalysts 2020, 10(10), 1211; https://doi.org/10.3390/catal10101211 - 19 Oct 2020
Cited by 2 | Viewed by 545
Abstract
Arylidene-Δ2-pyrrolin-4-ones undergo organocatalyzed double spirocyclization with 3-isothiocianato oxindoles in a domino 1,4/1,2-addition sequence. The products contain three contiguous stereocenters (ee up to 98%, dr up to 99:1, 12 examples). The absolute configuration of the major diastereomer was determined by single [...] Read more.
Arylidene-Δ2-pyrrolin-4-ones undergo organocatalyzed double spirocyclization with 3-isothiocianato oxindoles in a domino 1,4/1,2-addition sequence. The products contain three contiguous stereocenters (ee up to 98%, dr up to 99:1, 12 examples). The absolute configuration of the major diastereomer was determined by single crystal X-ray analysis. Along with heterocyclic Michael acceptors based on oxazolone, isoxazolone, thiazolidinone, pyrazolone, and pyrimidinedione, the reported results display the applicability of unsaturated Δ2-pyrrolin-4-ones (pyrrolones) for the organocatalyzed construction of 3D-rich pyrrolone-containing heterocycles. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Article
Stereoselective ROP of rac- and meso-Lactides Using Achiral TBD as Catalyst
Catalysts 2020, 10(6), 620; https://doi.org/10.3390/catal10060620 - 03 Jun 2020
Cited by 6 | Viewed by 945
Abstract
1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) polymerizes rac-lactide (rac-LA) to form highly isotactic polylactide (PLA) with a Pm = 0.88, while meso-LA yields heterotactic PLA (Pm ~ 0.8) at −75 °C. The stereocontrol of the cryogenic-based ring-opening polymerization comes from [...] Read more.
1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) polymerizes rac-lactide (rac-LA) to form highly isotactic polylactide (PLA) with a Pm = 0.88, while meso-LA yields heterotactic PLA (Pm ~ 0.8) at −75 °C. The stereocontrol of the cryogenic-based ring-opening polymerization comes from a perfect imbrication of both chiral LA and the propagating chiral end-group interacting with the achiral TBD catalyst. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Article
ADMET Polymerization of Dimeric Cinchona Squaramides for the Preparation of a Highly Enantioselective Polymeric Organocatalyst
Catalysts 2020, 10(5), 591; https://doi.org/10.3390/catal10050591 - 25 May 2020
Viewed by 795
Abstract
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 ( [...] Read more.
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. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Review

Jump to: Research

Review
Catalytic Foldamers: When the Structure Guides the Function
Catalysts 2020, 10(6), 700; https://doi.org/10.3390/catal10060700 - 22 Jun 2020
Cited by 5 | Viewed by 1080
Abstract
Enzymes are predominantly proteins able to effectively and selectively catalyze highly complex biochemical reactions in mild reaction conditions. Nevertheless, they are limited to the arsenal of reactions that have emerged during natural evolution in compliance with their intrinsic nature, three-dimensional structures and dynamics. [...] Read more.
Enzymes are predominantly proteins able to effectively and selectively catalyze highly complex biochemical reactions in mild reaction conditions. Nevertheless, they are limited to the arsenal of reactions that have emerged during natural evolution in compliance with their intrinsic nature, three-dimensional structures and dynamics. They optimally work in physiological conditions for a limited range of reactions, and thus exhibit a low tolerance for solvent and temperature conditions. The de novo design of synthetic highly stable enzymes able to catalyze a broad range of chemical reactions in variable conditions is a great challenge, which requires the development of programmable and finely tunable artificial tools. Interestingly, over the last two decades, chemists developed protein secondary structure mimics to achieve some desirable features of proteins, which are able to interfere with the biological processes. Such non-natural oligomers, so called foldamers, can adopt highly stable and predictable architectures and have extensively demonstrated their attractiveness for widespread applications in fields from biomedical to material science. Foldamer science was more recently considered to provide original solutions to the de novo design of artificial enzymes. This review covers recent developments related to peptidomimetic foldamers with catalytic properties and the principles that have guided their design. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Review
New Trends in Enantioselective Cross-Dehydrogenative Coupling
Catalysts 2020, 10(5), 529; https://doi.org/10.3390/catal10050529 - 11 May 2020
Cited by 8 | Viewed by 1188
Abstract
The development of cross-dehydrogenative coupling in recent years has simplified the synthesis of many materials, as a result of facile C–H activation, which, together with its greater atom economy and environmental friendliness, has made an impact on modern organic chemistry. Indeed, many C–C [...] Read more.
The development of cross-dehydrogenative coupling in recent years has simplified the synthesis of many materials, as a result of facile C–H activation, which, together with its greater atom economy and environmental friendliness, has made an impact on modern organic chemistry. Indeed, many C–C and C–X (X = N, O, P, S, B, or Si) coupling reactions can now be performed directly between two C–H bonds or a C–H and an X–H bond, simply by adding catalytic amounts of a metal salt to a mixture of the two and an oxidant to accept the two hydrogen atoms released. Chiral organocatalysts or chiral ligands have been joined to promote enantioselective processes, resulting in the development of efficient reaction cascades that provide products in high yields and high levels of asymmetric induction through cooperative catalysis. In recent years, photochemical oxidation and electrochemistry have widened even more the scope of cross-dehydrogenative coupling (CDC). In this review, we summarized the recent literature in this subject, hoping that it will inspire many new synthetic strategies. Full article
(This article belongs to the Special Issue Organocatalysis: Advances, Opportunity, and Challenges)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

 

Title: Organocatalysis in lipidic microcompartments as a prebiotic systems chemistry scenario: an inspiration for synthetic organic reactions?
Authors: Tecla Gasperi and Pasquale Stano
Abstract: An interesting scenario in prebiotic chemistry are the spontaneously formed vesicles that host organocatalytic reactions in their hydrophobic membrane. The latter can influence chemical reactions, acting as a promoter or regulator thanks to the multiple interactions established with substrates, products and catalysts. The general concepts on micellar catalysis are initially introduced and then adapted to the case of vesicles, highlighting similarities and differences. The organocatalytic reactions, which are increasingly important in synthetic organic chemistry, are particularly relevant in a primitive context, provided that multifunctional easy-to-form organic substances are available and that they bind to the membranes together with the substrates. In this regard, short peptides are interesting candidates. Although focused on primitive chemistry, the review also promotes organocatalytic reactions in hydrophobic microphases as a modern tool in green chemistry.

Title: Chitosan-Supported Cinchona Urea: Sustainable Organocatalyst for Asymmetric Michael Reaction
Authors: Shinichi Itsuno
Affiliation: Department of Applied Chemistry & Life Science Division of Molecular Chemistry Toyohashi University of Technology
Abstract: Novel chitosan-supported cinchona urea has been developed as heterogeneous catalysts for asymmetric reaction. The catalytic activity of the chitosan-supported organocatalyst was examined in asymmetric Michael addition reaction to give the chiral adducts in good yields with excellent enantionselectivities (up to 99% ee). The insolubility of the chitosan-supported cinchona urea catalyst facilitated the recovery of the catalyst. The catalyst was easily separated and reused without any loss of the catalytic activity.

Title: Catalytic foldamer: when the structure guides the function
Authors: Ludovic Maillard
Affiliation: Faculty of Pharmacy, Montpellier University

Title: Stereoselective ROP of rac- and meso-Lactides using Achiral TBD as Catalyst
Authors: Olivier Coulembier
Affiliation: Univ Mons, Lab Polymer & Composite Mat, CIRMAP, Pl Parc 23, B-7000 Mons, Belgium.
Abstract: TBD polymerizes rac-LA to form highly isotactic PLA, while meso-LA yields heterotactic PLA at -75 °C. The stereocontrol of the cryogenic-based ROP comes from a perfect imbrication of both chiral LA and the propagating chiral end-group interacting with the achiral TBD catalyst.

Title: Asymmetric Organocatalysed Michael Addition of masked Acetaldehyde to Nitro Alkenes
Authors: Armando Carlone
Affiliation: Department of Physical and Chemical Sciences, Università degli Studi dell'Aquila, via Vetoio, 67100 L'Aquila, Italy
Abstract: An enantioselective Michael addition of acetaldehyde to nitroalkenes catalyzed by the Hayashi-Jorgensen catalyst has been developed. Acetaldehyde is released in situ from a masked equivalent, allowing to reduce the equivalents needed. Using the described methodology, the synthesis of pharmacologically active compounds has been demonstrated.

Title: Mechanistic differences between boronic acids and organotrifluoroborates in diol-catalyzed conjugate additions
Authors: Jeremy A. May
Affiliation: Department of Chemistry, University of Houston
Abstract: Hammett plot analysis has shown differing influences of substrates when using boronic acids or organotrifluoroborates as nucleophiles. These differences suggest subtle mechanistic differences that reflect stabilizing effects on relative transition state energies. Additional mechanistic controls shed light on how the heterogeneity of the trifluoroborate salts impact reaction rates.

Title: Flow-through macroporous polymeric monoliths containing artificial catalytic centers mimicking chymotrypsin active site
Authors: Mariia Stepanova, Olga Solomakha, Daria Ten and Evgenia Korzhikova-Vlakh
Affiliation: Institute of Chemistry, Saint-Petersburg State University, Universitetsky pr. 26, 198504 St. Petersburg, Russia
Abstract: The synthetic catalysts which could compete with enzymes in term of the catalytic efficiency but surpass them in stability have a great potential for the practical application. In this work, we developed a novel kind of organic catalysts based on flow-through macroporous polymer monoliths containing catalytic centers mimicking the catalytic site of natural enzyme chymotrypsin. It is known that chymotrypsin catalytic center consists of L-serine, L-histidine and L-aspartic acid, and has specificity to C-terminal residues of hydrophobic amino acids (L-phenylalanine, L-tyrosine and L-tryptophan). In present work we prepared the macroporous polymer monoliths bearing grafted polymer layer on their surface. The last one was synthesized via copolymerization of N-methacryloyl-L-serine, N-methacryloyl-L-histidine, N-methacryloyl-L-aspartic acid. The spatial orientation of amino acids in the polymer layer, generated on the surface of monolithic framework, was achieved through the coordination of amino acid-polymerizable derivatives with cobalt (II) ions without substrate-mimicking template and with its use. The conditions for the preparation of mimetic materials were optimized to achieve the mechanically stable system. Catalytic properties of the developed systems were evaluated towards the hydrolysis of ester bond in low molecular substrate and compared with the results on the use of chymotrypsin immobilized on the surface of similar monolithic framework. For material prepared with the use of both cobalt (II) ions and template for catalytic centers generation, the catalytic activity kept constant even after 25 catalytic cycles that indicates high regeneration of catalyst after usage and good stability of artificial catalytic sites.

Title: First Organocatalytic Atroposelective Synthesis of Axially Chiral 1,4-Dihydropyridine Derivatives
Authors: Sandra Ardevines, Fernando Auria-Luna, Eugenia Marqués-López and Raquel P. Herrera
Affiliation: Laboratorio de Organocatálisis Asimétrica, Departamento de Química Orgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) CSIC-Universidad de Zaragoza, C/Pedro Cerbuna 12, Zaragoza 50009, Spain
Abstract: The enantioselective construction of axially chiral aryl skeletons is of great interest and an active challenging aim in organic synthesis. Based on our pioneering works for the enantioselective preparation of highly functionalized 1,4-dihydropyridines, we realized about the possibility of obtaining atropisomers from these scaffolds. Therefore, here we disclose the preliminary results concerning the first organocatalytic atroposelective synthesis of axially chiral 1,4-dihydropyridine derivatives. Moreover, our research could represent a pivotal example in this field for the construction of these appealing structural cores.

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