Topical Collection "Advanced Research Papers in Organics"

Editors

Prof. Dr. Wim Dehaen
E-Mail Website
Collection Editor
Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Leuven Chem&Tech, Celestijnenlaan 200F, B-3001 Leuven, Belgium
Interests: organic chemistry; heterocyclic chemistry; supramolecular chemistry
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Michal Szostak
E-Mail Website
Collection Editor
Department of Chemistry, Rutgers University, 73 Warren St, Newark, NJ 07102, USA
Interests: amide bonds; N-heterocyclic carbenes; C-N activation; C-H activation; C-O activation; lanthanides; cross-coupling; catalysis; reductions; reductive couplings; radical chemistry; synthetic methodology; natural products
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Huaping Xu
E-Mail Website
Collection Editor
Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, China
Interests: redox responsive polymers
Special Issues, Collections and Topics in MDPI journals

Topical Collection Information

Dear Colleagues,

We are pleased to announce that the Special Issue entitled "Feature Papers in Organics" is now open for submissions, which will be published, free of charge, in open access format after a peer-review process. We welcome contributions of high-quality manuscripts from Editorial Board Members, and from outstanding scholars invited by the Academic Editors and the Editorial Office. There is flexibility in the types of manuscript we will accept, and they include original research articles, short communications, highlights of new developments, and insightful critical reviews. Detailed experimental procedures are required for research articles and communications.

As shown by the keywords list, the sample research topics included in this Special Issue represent the whole journal; this is intended to provide an opportunity for manuscripts related to organic chemistry around the world to be submitted.

Prof. Dr. Wim Dehaen
Prof. Dr. Michal Szostak
Prof. Dr. Huaping Xu
Collection Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the collection website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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. Organics is an international peer-reviewed open access quarterly 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 1000 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

  • organic synthesis
  • development of synthetic methodology
  • theoretical organic chemistry
  • physical organic chemistry
  • supramolecular and macromolecular chemistry
  • heterocyclic chemistry
  • organocatalysis
  • bioorganic chemistry
  • organometallic chemistry
  • functional organic materials.

Published Papers (12 papers)

2022

Article
Theoretical Study on the Diels–Alder Reaction of Fullerenes: Analysis of Isomerism, Aromaticity, and Solvation
Organics 2022, 3(4), 364-379; https://doi.org/10.3390/org3040025 - 22 Sep 2022
Viewed by 297
Abstract
Fullerenes are reactive as dienophiles in Diels–Alder reactions. Their distinctive molecular shape and properties result in interesting and sometimes elusive reaction patterns. Herein, to contribute to the understanding of fullerene reactivity, we evaluate the energies of reactions for Diels–Alder cycloadditions of C60 [...] Read more.
Fullerenes are reactive as dienophiles in Diels–Alder reactions. Their distinctive molecular shape and properties result in interesting and sometimes elusive reaction patterns. Herein, to contribute to the understanding of fullerene reactivity, we evaluate the energies of reactions for Diels–Alder cycloadditions of C60, C70, and IC60MA with anthracene (Ant), by means of DFT computational analysis in vacuum and solution. The methods used showed little differentiation between the reactivity of the different fullerenes. The C70-Ant adducts where addition takes place near the edge of the fullerene were found to be the most stable regioisomers. For the IC60MA-Ant adducts, the calculated energies of reaction increase in the order: equatorial > trans-3 > trans-2 ≈ trans-4 ≈ trans-1 > cis-3 > cis-2. The change in the functional suggests the existence of stabilizing dispersive interactions between the surface of the fullerene and the addends. HOMA (harmonic oscillator model of aromaticity) analysis indicated an increase in aromaticity in the fullerene hexagons adjacent to the bonded addend. This increase is bigger in the rings of bisadduct isomers that are simultaneously adjacent to both addends, which helps explain the extra stability of the equatorial isomers. Solvation by m-xylene decreases the exothermicity of the reactions studied but has little distinguishing effect on the possible isomers. Thermal corrections reduce the exothermicity of the reactions by ~10 kJ∙mol−1. Full article
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Review
Recent Developments in Stereoselective Reactions of Sulfonium Ylides
Organics 2022, 3(3), 320-363; https://doi.org/10.3390/org3030024 - 15 Sep 2022
Viewed by 205
Abstract
This review describes advances in the literature since the mid-1990s in the area of reactions of sulfonium ylide chemistry, with particular attention paid to stereoselective examples. Although the chemistry of sulfonium ylides was first popularized and applied in a substantial way in the [...] Read more.
This review describes advances in the literature since the mid-1990s in the area of reactions of sulfonium ylide chemistry, with particular attention paid to stereoselective examples. Although the chemistry of sulfonium ylides was first popularized and applied in a substantial way in the 1960s, there has been sustained interest in the chemistry of sulfonium ylides since then. Many new ways of exploiting sulfonium ylides in productive stereoselective methodologies have emerged, often taking advantage of advances in organocatalysis and transition metal catalysis, to access stereodefined structurally complex motifs. The development of many different chiral sulfides over the last 20–30 years has also played a role in accelerating their study in a variety of reaction settings. In general, formal cycloaddition reactions ([2 + 1] and [4 + 1]) of sulfonium ylides follow a similar mechanistic pathway: initial addition of the nucleophilic ylide carbanion to an electrophile to form a zwitterionic betaine intermediate, followed by cyclization of the zwitterionic intermediate to afford the desired three-membered cyclic product (e.g., epoxide, cyclopropane, or aziridine), five-membered monocyclic (e.g., oxazolidinone), or fused bicyclic product (e.g., benzofuran, indoline). Full article
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Article
Unveiling the Origin of the Selectivity and the Molecular Mechanism in the [3+2] Cycloaddition Reaction of N-aryl-C-carbamoylnitrone with N-arylitaconimide
Organics 2022, 3(3), 281-292; https://doi.org/10.3390/org3030021 - 02 Sep 2022
Viewed by 173
Abstract
The [3+2] cycloaddition reaction of N-aryl-C-carbamoylnitrone (nitrone 1) with N-arylitaconimide (ethylene 2) was computationally studied using the B3LYP/6-31G(d) level of theory. An analysis of the different energetic profiles and the transition states’ optimized structures clearly indicated that this 32CA occurred through [...] Read more.
The [3+2] cycloaddition reaction of N-aryl-C-carbamoylnitrone (nitrone 1) with N-arylitaconimide (ethylene 2) was computationally studied using the B3LYP/6-31G(d) level of theory. An analysis of the different energetic profiles and the transition states’ optimized structures clearly indicated that this 32CA occurred through a non-polar, asynchronous, one-step mechanism, favoring the formation of the orthoendo cycloadduct, as observed experimentally. The analysis of the reactivity indices derived from the conceptual DFT explains well the low polarity of this 32CA reaction. Parr functions and a dual reactivity descriptors analysis correctly explained the regioselectivity ortho of this 32CA reaction. Solvent effects did not modify the obtained selectivity but it increased the activation energies and decreased the exothermic character of this 32CA reaction. A thermodynamic parameters analysis indicated that this 32CA wascharacterized by an ortho regioselectivity and endostereoselectivity and exothermic and exergonic characters. Full article
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Communication
An Unexpected Reaction between Diaryliodonium Salts and DMSO
Organics 2022, 3(3), 275-280; https://doi.org/10.3390/org3030020 - 31 Aug 2022
Viewed by 208
Abstract
Diaryliodonium salts are useful arylating reagents that have been exploited widely. In this Communication, we demonstrate that heating diphenyliodonium triflate in the solvent DMSO leads to an unexpected arylation reaction. It is postulated that arylation of DMSO at oxygen, followed by a thia-Sommelet–Hauser [...] Read more.
Diaryliodonium salts are useful arylating reagents that have been exploited widely. In this Communication, we demonstrate that heating diphenyliodonium triflate in the solvent DMSO leads to an unexpected arylation reaction. It is postulated that arylation of DMSO at oxygen, followed by a thia-Sommelet–Hauser rearrangement, leads to the formation of 2-thiomethylphenols. More substituted diaryliodonium salts and cyclic diaryliodonium salts are shown to be more stable and less likely to react with DMSO. In conclusion, when using iodonium salts dissolved in DMSO, beware of side-reactions. Full article
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Review
Palladium-Catalyzed Cross-Coupling Reactions of Borylated Alkenes for the Stereoselective Synthesis of Tetrasubstituted Double Bond
Organics 2022, 3(3), 210-239; https://doi.org/10.3390/org3030017 - 20 Jul 2022
Viewed by 325
Abstract
The stereoselective formation of tetrasubstituted alkenes remains one of the key goals of modern organic synthesis. In addition to other methods, the stereoselective synthesis of tetrasubstituted alkenes can be achieved by means of cross-coupling reactions of electrophilic and nucleophilic alkene templates. The use [...] Read more.
The stereoselective formation of tetrasubstituted alkenes remains one of the key goals of modern organic synthesis. In addition to other methods, the stereoselective synthesis of tetrasubstituted alkenes can be achieved by means of cross-coupling reactions of electrophilic and nucleophilic alkene templates. The use of electrophilic templates for the stereoselective synthesis of tetrasubstituted alkenes has previously been described. Therefore, the present review summarizes the procedures available for the stereoselective preparation of tetrasubstituted alkenes using stable and isolable nucleophilic templates. Full article
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Article
Synthesis and Theoretical Studies of Aromatic Azaborines
Organics 2022, 3(3), 196-209; https://doi.org/10.3390/org3030016 - 11 Jul 2022
Viewed by 316
Abstract
Organoboron compounds are well known for their use as synthetic building blocks in several significant reactions, e.g., palladium-catalyzed Suzuki-Miyaura cross-coupling. As an element, boron is fascinating; as part of a molecule it structurally resembles a three-valent atom, but if there is a lone [...] Read more.
Organoboron compounds are well known for their use as synthetic building blocks in several significant reactions, e.g., palladium-catalyzed Suzuki-Miyaura cross-coupling. As an element, boron is fascinating; as part of a molecule it structurally resembles a three-valent atom, but if there is a lone pair of electrons nearby, the boron atom’s empty p-orbital may capture the lone pair and form a covalent bond. This is the main aspect that is challenging chemistry during the synthesis of boron containing molecules and may lead into unexpected reactions and products. To study this, we synthesized and studied novel aromatic azaborines for better understanding of their structures and reactions. Here, we report a one-pot method for the synthesis of substituted aromatic azaborines and computational studies of their structure to explain their observed chemical properties. Full article
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Article
Regioselective Transfer Hydrogenative Defluorination of Polyfluoroarenes Catalyzed by Bifunctional Azairidacycle
Organics 2022, 3(3), 150-160; https://doi.org/10.3390/org3030012 - 22 Jun 2022
Viewed by 406
Abstract
The catalytic hydrodefluorination (HDF) with a bifunctional azairidacycle using HCOOK was examined for cyano- and chloro-substituted fluoroarenes, including penta- and tetrafluorobenzonitriles, tetrafluoroterephthalonitrile, tetrafluorophthalonitrile, 3-chloro-2,4,5,6-tetrafluoropyridine, and 4-cyano-2,3,5,6-tetrafluoropyridine. The reaction was performed in the presence of a controlled amount of HCOOK with a substrate/catalyst ratio [...] Read more.
The catalytic hydrodefluorination (HDF) with a bifunctional azairidacycle using HCOOK was examined for cyano- and chloro-substituted fluoroarenes, including penta- and tetrafluorobenzonitriles, tetrafluoroterephthalonitrile, tetrafluorophthalonitrile, 3-chloro-2,4,5,6-tetrafluoropyridine, and 4-cyano-2,3,5,6-tetrafluoropyridine. The reaction was performed in the presence of a controlled amount of HCOOK with a substrate/catalyst ratio (S/C) of 100 in a 1:1 mixture of 1,2-dimethoxyethane (DME) and H2O at an ambient temperature of 30 °C to obtain partially fluorinated compounds with satisfactory regioselectivities. The C–F bond cleavage proceeded favorably at the para position of substituents other than fluorine, which is in consonance with the nucleophilic aromatic substitution mechanism. In the HDF of tetrafluoroterephthalonitrile and 4-cyano-2,3,5,6-tetrafluoropyridine, which do not contain a fluorine atom at the para position of the cyano group, the double defluorination occurred solely at the 2- and 5-positions, as confirmed by X-ray crystallography. The HDF of 3-chloro-2,4,5,6-tetrafluoropyridine gave preference to the C–F bond cleavage over the C–Cl bond cleavage, unlike the dehalogenation pathway via electron-transfer radical anion fragmentation. In addition, new azairidacycles with an electron-donating methoxy substituent on the C–N chelating ligand were synthesized and served as a catalyst precursor (0.2 mol%) for the transfer hydrogenative defluorination of pentafluoropyridine, leading to 2,3,5,6-tetrafluoropyridine with up to a turnover number (TON) of 418. Full article
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Article
Synthesis of Amino-Acid-Based Nitroalkenes
Organics 2022, 3(2), 137-149; https://doi.org/10.3390/org3020011 - 14 Jun 2022
Viewed by 416
Abstract
Fatty-acid-based nitroalkenes have recently received great attention because of their bioactivities. On the contrary, peptide- or amino-acid-based nitroalkenes have been scarcely explored so far, although they may exhibit interesting biological properties, for example, as enzyme inhibitors. In this work, we study protocols for [...] Read more.
Fatty-acid-based nitroalkenes have recently received great attention because of their bioactivities. On the contrary, peptide- or amino-acid-based nitroalkenes have been scarcely explored so far, although they may exhibit interesting biological properties, for example, as enzyme inhibitors. In this work, we study protocols for the efficient synthesis of nitroalkenes based on natural amino acids. A variety of N-protected amino alcohols and Weinreb amides, derived from α-amino acids, were converted to the corresponding N-protected amino aldehydes, and, through a Henry reaction with nitroalkanes, produced the corresponding nitro alcohols. The subsequent elimination reaction led to the (E)-isomer of amino-acid-based nitroalkenes in moderate to high yields. Full article
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Article
Acid Catalyzed N-Alkylation of Pyrazoles with Trichloroacetimidates
Organics 2022, 3(2), 111-121; https://doi.org/10.3390/org3020009 - 24 May 2022
Viewed by 398
Abstract
N-Alkyl pyrazoles are important heterocycles in organic and medicinal chemistry, demonstrating a wide range of biological activity. A new method for the N-alkylation of pyrazoles has been developed using trichloroacetimidate electrophiles and a Brønsted acid catalyst. These reactions provide ready access [...] Read more.
N-Alkyl pyrazoles are important heterocycles in organic and medicinal chemistry, demonstrating a wide range of biological activity. A new method for the N-alkylation of pyrazoles has been developed using trichloroacetimidate electrophiles and a Brønsted acid catalyst. These reactions provide ready access to N-alkyl pyrazoles which are present in a variety of medicinally relevant lead structures. Benzylic, phenethyl and benzhydryl trichloroacetimidates provide good yields of the N-alkyl pyrazole products. Unsymmetrical pyrazoles provide a mixture of the two possible regioisomers, with the major product being controlled by sterics. This methodology provides an alternative to other alkylation methods that require strong base or high temperature. Full article
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Article
A Theoretical Study on the Photochemical Isomerization of 2,6-Dimethylpyrazine
Organics 2022, 3(2), 95-101; https://doi.org/10.3390/org3020007 - 12 May 2022
Viewed by 368
Abstract
DFT calculations on the photoisomerization of 2,6-dimethylpyrazine allowed us to confirm the role of benzvalene isomers in the isomerization of hexatomic heterocyclic compounds. 2,6-Dimethylpyrazine in the excited singlet states can be converted into the corresponding Dewar isomers. If the S2 state is [...] Read more.
DFT calculations on the photoisomerization of 2,6-dimethylpyrazine allowed us to confirm the role of benzvalene isomers in the isomerization of hexatomic heterocyclic compounds. 2,6-Dimethylpyrazine in the excited singlet states can be converted into the corresponding Dewar isomers. If the S2 state is populated, two Dewar isomers can be obtained, while the S1 state allows the formation of only one of the possible Dewar isomers. Both Dewar isomers can be converted into the benzvalene isomer, that is, the precursor of 4,5-dimethylpyrimidine, the reaction product. In fact, the benzvalene isomer can be obtained from the Dewar isomers in processes that occur without an activation energy, and it is the more stable benzvalene isomers that can be obtained from the Dewar isomers. CASSCF study indicates the presence of a conical intersection allowing the direct formation of the benzvalene isomer. Full article
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Article
Stabilized Arylzinc Iodides in Negishi Acylative Cross-Coupling: A Modular Synthesis of Chalcones
Organics 2022, 3(2), 87-94; https://doi.org/10.3390/org3020006 - 23 Apr 2022
Viewed by 636
Abstract
Stabilized arylzinc iodides, synthesized by direct insertion of zinc into the corresponding halides, were used as nucleophiles into an acylative Negishi coupling reaction to synthesize chalcones. The reaction conditions were optimized to afford optimal results on a model reaction and then applied to [...] Read more.
Stabilized arylzinc iodides, synthesized by direct insertion of zinc into the corresponding halides, were used as nucleophiles into an acylative Negishi coupling reaction to synthesize chalcones. The reaction conditions were optimized to afford optimal results on a model reaction and then applied to synthesize nine compounds. Esters, chlorides, electron-rich, electron-poor and sterically hindered substrates are well tolerated and even heteroaryl derivatives can be synthesized. Full article
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Article
De Novo Synthesis of Bacteriochlorins Bearing Four Trideuteriomethyl Groups
Organics 2022, 3(1), 22-37; https://doi.org/10.3390/org3010002 - 07 Feb 2022
Viewed by 745
Abstract
Site-specific introduction of isotopes in tetrapyrrole macrocycles provides the foundation for probing physicochemical features germane to photosynthetic energy-transduction processes, but has chiefly been done with porphyrins rather than the more biologically relevant hydroporphyrin analogues of native photosynthetic pigments. A prior study incorporated pairwise [...] Read more.
Site-specific introduction of isotopes in tetrapyrrole macrocycles provides the foundation for probing physicochemical features germane to photosynthetic energy-transduction processes, but has chiefly been done with porphyrins rather than the more biologically relevant hydroporphyrin analogues of native photosynthetic pigments. A prior study incorporated pairwise 13C or 15N atoms in the skeleton of a bacteriochlorin containing a gem-dimethyl group in each pyrroline ring. Here, a complementary effort is reported that installs deuterium atoms in substituents at the perimeter of a bacteriochlorin. Thus, perdeuteriated 3-methyl-2,4-pentanedione was converted in an 8-step synthesis via the intermediacy of tert-butyl 5-formyl-3,4-bis(trideuteriomethyl)pyrrole-2-carboxylate to the 2,3,12,13-tetrakis(trideuteriomethyl)-8,8,18,18-tetramethylbacteriochlorin (BC-2). The fidelity of isotope substitution was maintained throughout the synthesis. Resonance Raman spectroscopy of the copper chelate (CuBC-2) revealed that addition of the four β-pyrrolic substituents alone is not sufficient to account for the vibronic complexity observed for the copper chelate of bacteriochlorophyll a (CuBChl a). The increased vibronic activity exhibited by the natural pigments and CuBChl a must arise from the increased structural complexity of the macrocycle. Full article
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