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Diels-Alder Reaction in Organic Synthesis
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Diels-Alder Reaction in Organic Synthesis

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 July 2021) | Viewed by 25019

Special Issue Editors

Prof. Dr. Teresa Pinho e Melo

E-Mail Website
Guest Editor
Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal
Interests: organic synthesis; synthetic and mechanistic heterocyclic chemistry; new synthetic methods; medicinal chemistry
Dr. Maria Isabel L. Soares

E-Mail Website
Guest Editor
Department of Chemistry, Coimbra Chemistry Centre–Institute of Molecular Sciences, University of Coimbra, 3004-535 Coimbra, Portugal
Interests: organic synthesis; heterocyclic chemistry; medicinal chemistry; oxygen heterocycles; allenes; cycloaddition reactions; annulation reactions; flash vacuum pyrolysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The Diels–Alder reaction is one of the most effective and reliable strategies for the construction of six-membered carbocyclic and heterocyclic rings. Since the seminal work of Otto Diels and Kurt Alder in 1928, the advances and developments of the Diels–Alder reaction, as well as extensive mechanistic and computational studies, have emerged at an impressive rate. The high regio- and stereoselectivity of the Diels–Alder reaction and its versatility, mainly due to the available panoply of dienes and dienophiles, including heterodienes and heterodienophiles, make it a powerful tool for organic chemists. Furthermore, the asymmetric Diels–Alder reaction has become an important synthetic approach to optically active six-membered rings. Despite the enormous advances in this area, from asymmetric Diels–Alder reaction to total synthesis of drugs and natural products, new contributions continue to be reported.

This Special Issue on “Diels–Alder Reaction in Organic Synthesis” aims to bring together the latest developments on this topic. Full papers, communications, and reviews are all welcome for submission.

Prof. Dr. Teresa Pinho e Melo
Dr. Maria Isabel L. Soares
Guest 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 special issue 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. Molecules is an international peer-reviewed open access semimonthly 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 2700 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

  • Diels−Alder reactions
  • Hetero-Diels–Alder reactions
  • Asymmetric Diels–Alder reactions
  • Carbocyclic compounds
  • Heterocycles
  • Heterodienophiles
  • Heterodienes
  • Natural product synthesis
  • Mechanistic studies
  • Sustainable organic synthesis
  • Nonconventional reaction media
  • Microwaves
  • Sonication
  • Mechanochemistry
  • Flow chemistry

Published Papers (7 papers)

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Research

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15 pages, 2583 KiB  
Article
Synthesis of the [11]Cyclacene Framework by Repetitive Diels–Alder Cycloadditions
by John B. Bauer, Fatima Diab, Cäcilia Maichle-Mössmer, Hartmut Schubert and Holger F. Bettinger
Molecules 2021, 26(10), 3047; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26103047 - 20 May 2021
Cited by 1 | Viewed by 2576
Abstract
The Diels–Alder cycloaddition between bisdienes and bisdienophile incorporating the 7-oxa-bicyclo[2.2.1]heptane unit are well known to show high diastereoselectivity that can be exploited for the synthesis of molecular belts. The related bisdiene 5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octene is a valuable building block for the synthesis of photoprecursors for [...] Read more.
The Diels–Alder cycloaddition between bisdienes and bisdienophile incorporating the 7-oxa-bicyclo[2.2.1]heptane unit are well known to show high diastereoselectivity that can be exploited for the synthesis of molecular belts. The related bisdiene 5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octene is a valuable building block for the synthesis of photoprecursors for acenes, but it has not been employed for the synthesis of molecular belts. The present work investigates by computational means the Diels–Alder reaction between these bisdiene building blocks with syn-1,4,5,8-tetrahydro-1,4:5,8-diepoxyanthracene, which shows that the diastereoselectivity of the Diels–Alder reaction of the etheno-bridged bisdiene is lower than that of the epoxy-bridged bisdiene. The reaction of the etheno-bridged bisdiene and syn-1,4,5,8-tetrahydro-1,4:5,8-diepoxyanthracene in 2:1 ratio yields two diastereomers that differ in the orientation of the oxa and etheno bridges based on NMR and X-ray crystallography. The all-syn diastereomer can be transformed into a molecular belt by inter- and intramolecular Diels–Alder reactions with a bifunctional building block. The molecular belt could function as a synthetic intermediate en route to a [11]cyclacene photoprecursor. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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19 pages, 4058 KiB  
Article
Hetero-Diels-Alder Reactions of In Situ-Generated Azoalkenes with Thioketones; Experimental and Theoretical Studies
by Grzegorz Mlostoń, Katarzyna Urbaniak, Malwina Sobiecka, Heinz Heimgartner, Ernst-Ulrich Würthwein, Reinhold Zimmer, Dieter Lentz and Hans-Ulrich Reissig
Molecules 2021, 26(9), 2544; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26092544 - 27 Apr 2021
Cited by 10 | Viewed by 2822
Abstract
The hetero-Diels-Alder reactions of in situ-generated azoalkenes with thioketones were shown to offer a straightforward method for an efficient and regioselective synthesis of scarcely known N-substituted 1,3,4-thiadiazine derivatives. The scope of the method was fairly broad, allowing the use of a series [...] Read more.
The hetero-Diels-Alder reactions of in situ-generated azoalkenes with thioketones were shown to offer a straightforward method for an efficient and regioselective synthesis of scarcely known N-substituted 1,3,4-thiadiazine derivatives. The scope of the method was fairly broad, allowing the use of a series of aryl-, ferrocenyl-, and alkyl-substituted thioketones. However, in the case of N-tosyl-substituted cycloadducts derived from 1-thioxo-2,2,4,4-tetramethylcyclobutan-3-one and the structurally analogous 1,3-dithione, a more complicated pathway was observed. By elimination of toluene sulfinic acid, the initially formed cycloadducts afforded 2H-1,3,4-thiadiazines as final products. Advanced DFT calculations revealed that the observed high regioselectivity was due to kinetic reaction control and that the (4 + 2)-cycloadditions of sterically less unhindered thiones occurred via highly unsymmetric transition states with shorter C..S-distances (2.27–2.58 Å) and longer N..C-distances (3.02–3.57 Å). In the extreme case of the sterically very hindered 2,2,4,4-tetramethylcyclobutan-1,3-dione-derived thioketones, a zwitterionic intermediate with a fully formed C‒S bond was detected, which underwent ring closure to the 1,3,4-thiadiazine derivative in a second step. For the hypothetical formation of the regioisomeric 1,2,3-thiadiazine derivatives, the DFT calculations proposed more symmetric transition states with considerably higher energies. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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8 pages, 1827 KiB  
Communication
Maleimide Self-Reaction in Furan/Maleimide-Based Reversibly Crosslinked Polyketones: Processing Limitation or Potential Advantage?
by Felipe Orozco, Zafarjon Niyazov, Timon Garnier, Nicola Migliore, Alexander T. Zdvizhkov, Patrizio Raffa, Ignacio Moreno-Villoslada, Francesco Picchioni and Ranjita K. Bose
Molecules 2021, 26(8), 2230; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26082230 - 13 Apr 2021
Cited by 20 | Viewed by 3853
Abstract
Polymers crosslinked via furan/maleimide thermo-reversible chemistry have been extensively explored as reprocessable and self-healing thermosets and elastomers. For such applications, it is important that the thermo-reversible features are reproducible after many reprocessing and healing cycles. Therefore, side reactions are undesirable. However, we have [...] Read more.
Polymers crosslinked via furan/maleimide thermo-reversible chemistry have been extensively explored as reprocessable and self-healing thermosets and elastomers. For such applications, it is important that the thermo-reversible features are reproducible after many reprocessing and healing cycles. Therefore, side reactions are undesirable. However, we have noticed irreversible changes in the mechanical properties of such materials when exposing them to temperatures around 150 °C. In this work, we study whether these changes are due to the self-reaction of maleimide moieties that may take place at this rather low temperature. In order to do so, we prepared a furan-grafted polyketone crosslinked with the commonly used aromatic bismaleimide (1,1′-(methylenedi-4,1-phenylene)bismaleimide), and exposed it to isothermal treatments at 150 °C. The changes in the chemistry and thermo-mechanical properties were mainly studied by infrared spectroscopy, 1H-NMR, and rheology. Our results indicate that maleimide self-reaction does take place in the studied polymer system. This finding comes along with limitations over the reprocessing and self-healing procedures for furan/maleimide-based reversibly crosslinked polymers that present their softening (decrosslinking) point at relatively high temperatures. On the other hand, the side reaction can also be used to tune the properties of such polymer products via in situ thermal treatments. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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15 pages, 4016 KiB  
Article
Periselectivity in the Aza-Diels–Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study
by Marc Presset, Michel Rajzmann, Guillaume Dauvergne, Jean Rodriguez and Yoann Coquerel
Molecules 2020, 25(20), 4811; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25204811 - 20 Oct 2020
Cited by 1 | Viewed by 2321
Abstract
Inversions in the periselectivity of formal aza-Diels–Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the [...] Read more.
Inversions in the periselectivity of formal aza-Diels–Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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Review

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46 pages, 12924 KiB  
Review
Diels–Alder Cycloaddition Reactions in Sustainable Media
by Maria I. L. Soares, Ana L. Cardoso and Teresa M. V. D. Pinho e Melo
Molecules 2022, 27(4), 1304; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27041304 - 15 Feb 2022
Cited by 9 | Viewed by 5357
Abstract
Diels–Alder cycloaddition reaction is one of the most powerful strategies for the construction of six-membered carbocyclic and heterocyclic systems, in most cases with high regio- and stereoselectivity. In this review, an insight into the most relevant advances on sustainable Diels–Alder reactions since 2010 [...] Read more.
Diels–Alder cycloaddition reaction is one of the most powerful strategies for the construction of six-membered carbocyclic and heterocyclic systems, in most cases with high regio- and stereoselectivity. In this review, an insight into the most relevant advances on sustainable Diels–Alder reactions since 2010 is provided. Various environmentally benign solvent systems are discussed, namely bio-based derived solvents (such as glycerol and gluconic acid), polyethylene glycol, deep eutectic solvents, supercritical carbon dioxide, water and water-based aqueous systems. Issues such as method’s scope, efficiency, selectivity and reaction mechanism, as well as sustainability, advantages and limitations of these reaction media, are addressed. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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26 pages, 10508 KiB  
Review
Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings
by Michael J. McGlinchey
Molecules 2020, 25(20), 4730; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25204730 - 15 Oct 2020
Cited by 1 | Viewed by 2604
Abstract
The intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopentadienones, bearing ferrocenyl [...] Read more.
The intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopentadienones, bearing ferrocenyl and multiple phenyl or naphthyl substituents undergo [4 + 2] cycloadditions with diaryl acetylenes or triphenylcyclopropene to form the corresponding polyarylbenzenes or cycloheptatrienes. The heptaphenyltropylium cation, [C7Ph7+], was shown to adopt a nonplanar shallow boat conformation. In contrast, the attempted Diels-Alder reaction of tetracyclone and phenethynylfluorene yielded electroluminescent tetracenes. Finally, benzyne addition to 9-(2-indenyl)anthracene, and subsequent incorporation of a range of organometallic fragments, led to development of an organometallic molecular brake. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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23 pages, 6847 KiB  
Review
Boron and Silicon-Substituted 1,3-Dienes and Dienophiles and Their Use in Diels-Alder Reactions
by Mark E. Welker
Molecules 2020, 25(16), 3740; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25163740 - 16 Aug 2020
Cited by 12 | Viewed by 3680
Abstract
Boron and silicon-substituted 1,3-dienes and boron and silicon-substituted alkenes and alkynes have been known for years and the last 10 years have seen a number of new reports of their preparation and use in Diels-Alder reactions. This review first covers boron-substituted dienes and [...] Read more.
Boron and silicon-substituted 1,3-dienes and boron and silicon-substituted alkenes and alkynes have been known for years and the last 10 years have seen a number of new reports of their preparation and use in Diels-Alder reactions. This review first covers boron-substituted dienes and dienophiles and then moves on to discuss silicon-substituted dienes and dienophiles. Full article
(This article belongs to the Special Issue Diels-Alder Reaction in Organic Synthesis)
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