Special Issue "Molecules from Side Reactions II"

A special issue of Molbank (ISSN 1422-8599). This special issue belongs to the section "Organic Synthesis".

Deadline for manuscript submissions: 31 January 2023 | Viewed by 11797

Special Issue Editors

Dr. Stefano D’Errico
E-Mail Website
Guest Editor
Department of Pharmacy, University of Naples Federico II, Via Domenico Montesano 49, 80131 Naples, Italy
Interests: solid-phase synthesis; chemistry of nucleosides; nucleotides and oligonucleotides; L-sugars; platinum complexes
Special Issues, Collections and Topics in MDPI journals
Dr. Annalisa Guaragna
E-Mail Website
Guest Editor
Department of Chemical, Materials and Production Engineering, University of Naples Federico II, Piazzale V. Tecchio, 80, 80125 Naples, Italy
Interests: chemistry of nucleosides; nucleotides and oligonucleotides; L-sugars; iminosugars; cystic fibrosis disease
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

It is with great pleasure that the second edition of the Special Issue "Molecules from Side Reactions" is launched, following the success of the first edition. This Special Issue aims to make available to the scientific community information on the side reactions and side products that inevitably take place during total or multistep syntheses. The submission of research articles covering all of the fields of organic chemistry is welcome. Due to the special nature of this topic, the reaction yields are not a key element in assessing the quality of the submitted research.

You may choose our Joint Special Issue in Molecules.

Dr. Stefano D’Errico
Dr. Annalisa Guaragna
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. Molbank 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 500 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
  • Solid-phase synthesis
  • Heterocycles
  • Building blocks
  • Intermediates
  • Medicinal chemistry
  • Chemical diversity
  • Carbon–carbon bond formation
  • Metal-mediated reactions
  • Drug design

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Published Papers (9 papers)

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Research

Short Note
19β,28-Epoxy-18α-olean-3β-ol-2-furoate from Allobetulin (19β,28-Epoxy-18α-olean-3β-ol)
Molbank 2022, 2022(4), M1499; https://doi.org/10.3390/M1499 - 18 Nov 2022
Viewed by 261
Abstract
The E ring of betulin rearranges and forms a cyclic ether when treated with an acid. Treatment of betulin with iodine generated hydrogen iodide in situ, which went on to promote the rearrangement at C-19 and C-20, followed by cyclization to form allobetulin. [...] Read more.
The E ring of betulin rearranges and forms a cyclic ether when treated with an acid. Treatment of betulin with iodine generated hydrogen iodide in situ, which went on to promote the rearrangement at C-19 and C-20, followed by cyclization to form allobetulin. A reaction of allobetulin with 2-furoyl chloride yielded 19β,28-Epoxy-18α-olean-3β-ol-2-furoate. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Scheme 1

Short Note
Dichloro{4-(4-chlorophenoxy)phthalazin-1-yl} methylphosphonic dichloride
Molbank 2022, 2022(3), M1439; https://doi.org/10.3390/M1439 - 05 Sep 2022
Viewed by 649
Abstract
As part of our ongoing scaffold-hopping work on an antiplasmodial 2-trichloromethylquinazoline scaffold, we aimed to explore the 1-trichloromethylphthalazine scaffold as a potential new antimalarial series. Using previously chlorination conditions described by our lab to obtain a trichloromethyl group from a methyl group, we [...] Read more.
As part of our ongoing scaffold-hopping work on an antiplasmodial 2-trichloromethylquinazoline scaffold, we aimed to explore the 1-trichloromethylphthalazine scaffold as a potential new antimalarial series. Using previously chlorination conditions described by our lab to obtain a trichloromethyl group from a methyl group, we did not obtain the target compound; instead, we obtained a dichloro methylphosphonic dichloride side product 3. The nature of this compound was then characterized by NMR, HRMS and X-ray crystallography. The same issue was previously reported by Kato et al., starting from the 2-methyl-3-nitropyridine. Finally, compound 3, although not cytotoxic, was not active against P. falciparum, the parasite responsible for human malaria. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Figure 1

Short Note
O6-[(2″,3″-O-Isopropylidene-5″-O-tbutyldimethylsilyl)pentyl]-5′-O-tbutyldiphenylsilyl-2′,3′-O-isopropylideneinosine
Molbank 2022, 2022(1), M1345; https://doi.org/10.3390/M1345 - 01 Mar 2022
Cited by 1 | Viewed by 1634
Abstract
Cyclic adenosine diphosphate ribose (cADPR) is a cyclic nucleotide involved in the Ca2+ homeostasis. In its structure, the northern ribose, bonded to adenosine through an N1 glycosidic bond, is connected to the southern ribose through a pyrophosphate bridge. Due to the chemical [...] Read more.
Cyclic adenosine diphosphate ribose (cADPR) is a cyclic nucleotide involved in the Ca2+ homeostasis. In its structure, the northern ribose, bonded to adenosine through an N1 glycosidic bond, is connected to the southern ribose through a pyrophosphate bridge. Due to the chemical instability at the N1 glycosidic bond, new bioactive cADPR derivatives have been synthesized. One of the most interesting analogues is the cyclic inosine diphosphate ribose (cIDPR), in which the hypoxanthine replaced adenosine. The efforts for synthesizing new linear and cyclic northern ribose modified cIDPR analogues led us to study in detail the inosine N1 alkylation reaction. In the last few years, we have produced new flexible cIDPR analogues, where the northern ribose has been replaced by alkyl chains. With the aim to obtain the closest flexible cIDPR analogue, we have attached to the inosine N1 position a 2″,3″-dihydroxypentyl chain, possessing the two OH groups in a ribose-like fashion. The inosine alkylation reaction afforded also the O6-alkylated regioisomer, which could be a useful intermediate for the construction of new kinds of cADPR mimics. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Graphical abstract

Short Note
3-Isobutyl-5,5,7-tris(3-methylbut-2-en-1-yl)-1-phenyl-1,7-dihydro-4H-indazole-4,6(5H)-dione
Molbank 2022, 2022(1), M1330; https://doi.org/10.3390/M1330 - 01 Feb 2022
Viewed by 1041
Abstract
Here we describe the functionalization of lupulone natural compound in obtaining 3-isobutyl-5,5,7-tris(3-methylbut-2-en-1-yl)-1-phenyl-1,7-dihydro-4H-indazole-4,6(5H)-dione. The lupulone-H-indazole derivative was prepared with 75% yield through the reaction between lupulone and phenyl-hydrazine employing SiO2/ZnCl2 (30% m/m) [...] Read more.
Here we describe the functionalization of lupulone natural compound in obtaining 3-isobutyl-5,5,7-tris(3-methylbut-2-en-1-yl)-1-phenyl-1,7-dihydro-4H-indazole-4,6(5H)-dione. The lupulone-H-indazole derivative was prepared with 75% yield through the reaction between lupulone and phenyl-hydrazine employing SiO2/ZnCl2 (30% m/m) as a support solid in a solvent-free condition. Based on the possibilities of products, a complete NMR structural characterization of this lupulone-H-indazole was performed by 1H, 13C{1H}, COSY, HSQC and HMBC NMR experiments, showing an important contribution in producing the first results related to lupulone reactivity. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Figure 1

Short Note
Poly[3-methyl-1,3-oxazolidin-2-iminium[µ3-cyanido-tri-µ2-cyanido-κ9C:N-tricuprate(I)]]
Molbank 2021, 2021(3), M1259; https://doi.org/10.3390/M1259 - 26 Jul 2021
Viewed by 977
Abstract
The unexpected formation of an oxazole ring has occurred during synthesis of a copper(I) cyanide network polymer as part of our ongoing studies of the structural chemistry of these networks. Crystals of the title compound were formed during the synthesis of a previously [...] Read more.
The unexpected formation of an oxazole ring has occurred during synthesis of a copper(I) cyanide network polymer as part of our ongoing studies of the structural chemistry of these networks. Crystals of the title compound were formed during the synthesis of a previously reported CuCN network solid containing protonated N-methylethanolamine and have been characterized by single crystal X-ray structure analysis. The structure shows well-defined oxazole-2-iminium cations sitting in continuous channels along the short a-axis of the crystal in a new three-dimensional copper(I) cyanide polymeric network. Evidently, a reaction has occurred between the cyanide ion and the protonated N-methylethanolamine base. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Graphical abstract

Short Note
N,N-Bis(hexyl α-d-acetylmannosyl) Acrylamide
Molbank 2021, 2021(3), M1255; https://doi.org/10.3390/M1255 - 22 Jul 2021
Viewed by 1269
Abstract
Glycosyl monomers for the assembly of multivalent ligands are typically synthesized using carbohydrates with biological functions and polymerizable functional groups such as acrylamide or styrene introduced into the carbohydrate aglycon, and monomers polymerized using a radical initiator. Herein, we report the acryloylation of [...] Read more.
Glycosyl monomers for the assembly of multivalent ligands are typically synthesized using carbohydrates with biological functions and polymerizable functional groups such as acrylamide or styrene introduced into the carbohydrate aglycon, and monomers polymerized using a radical initiator. Herein, we report the acryloylation of 6-aminohexyl α-d-mannoside and its conversion into the glycosyl monomer bearing an acrylamide group. The general acryloylation procedure afforded the desired N-hexyl α-d-acetylmannosyl acrylamide monomer as well as an unexpected compound with a close Rf value. The compounds were separated and analyzed by nuclear magnetic resonance spectroscopy and mass spectrometry, which revealed the unknown compound to be the bivalent N,N-bis(hexyl α-d-acetylmannosyl) acrylamide monomer, which contains two hexyl mannose units and one acrylamide group. To the best of our knowledge, this side reaction has not previously been disclosed, and may be useful for the construction of multivalent sugar ligands. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Figure 1

Short Note
N-{2-[(3-Oxo-1,3-dihydro-2-benzofuran-1-yl)acetyl]phenyl}acetamide
Molbank 2021, 2021(3), M1244; https://doi.org/10.3390/M1244 - 02 Jul 2021
Viewed by 1274
Abstract
With the aim of obtaining different derivatives belonging to the isoindolo[2,1-a]quinoline family, we have synthesized a novel N-{2-[(3-oxo-1,3-dihydro-2-benzofuran-1-yl)acetyl]phenyl}acetamide derivative by a Claisen–Smichdt-type condensation reaction in 75% yield. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Figure 1

Communication
Unexpected Formation of 4-aryl-1-(Propane-2-ylidenehydrazono)-2,3-diazaspiro[5.5]undec-3-ene by the Reaction of Pyridazinethiones Derivatives with Hydrazine
Molbank 2021, 2021(3), M1243; https://doi.org/10.3390/M1243 - 02 Jul 2021
Viewed by 1270
Abstract
After making a new series of spiro[cycloalkane]pyridazinones with high Fsp3 character available, the new target was to synthesize derivatives comprising nitrogen-containing heterocycles, such as triazolo or tetrazolo rings. The corresponding thioxo derivatives (1a,b) seemed to be good starting [...] Read more.
After making a new series of spiro[cycloalkane]pyridazinones with high Fsp3 character available, the new target was to synthesize derivatives comprising nitrogen-containing heterocycles, such as triazolo or tetrazolo rings. The corresponding thioxo derivatives (1a,b) seemed to be good starting materials for the synthesis of tetrazolo derivatives. The reaction of the pyridazinethiones (1a,b) with hydrazine surprisingly resulted in Schiff bases (3a,b) deriving from the reaction of hydrazones (2a,b) with acetone. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Scheme 1

Communication
Unexpected Metal-Free Dehydrogenation of a β-Ketoester to a Phenol Using a Recyclable Oxoammonium Salt
Molbank 2021, 2021(1), M1180; https://doi.org/10.3390/M1180 - 13 Jan 2021
Cited by 2 | Viewed by 2024
Abstract
The conversion of ethyl 2-oxocyclohexanecarboxylate to ethyl salicylate using an oxoammonium salt is reported. The dehydrogenation reaction is operationally simple and compares favorably with previous literature examples for the same transformation and expands the scope of oxoammonium salts as reagents for oxidative functionalization [...] Read more.
The conversion of ethyl 2-oxocyclohexanecarboxylate to ethyl salicylate using an oxoammonium salt is reported. The dehydrogenation reaction is operationally simple and compares favorably with previous literature examples for the same transformation and expands the scope of oxoammonium salts as reagents for oxidative functionalization processes. Full article
(This article belongs to the Special Issue Molecules from Side Reactions II)
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Graphical abstract

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: 3-methylene-2,3-dihydronaphtho[2,3-b][1,4]dioxin-2-yl)methanol
Authors: Valentina Straniero
Affiliation: Department of Pharmaceutical Science, University of Milan, Via Luigi Mangiagalli, 25, 20133 Milano, Italy
Abstract: (3-methylene-2,3-dihydronaphtho[2,3-b][1,4]dioxin-2-yl)methanol was unexpectedly achieved as the main reaction product while applying a standard Johnson-Corey-Chaykovsky procedure to the 2,3-dihydronaphtho[2,3-b][1,4]dioxine-2-carbaldehyde, aiming at obtaining the corresponding epoxide. The structure of the recovered compound was confirmed through NMR and HRMS, the melting point measured by DSC and the organic purity assessed using HPLC. We hypothesized the possible mechanism for the obtainment of this side product, which should involve the opening of the dioxane ring, soon after the nucleophilic attack of the ylide to the carbonyl function. The consequent transfer of the negative charge let the achieving of the phenolate function. The prototropic tautomer further rearranges, forming the instable oxirane, which opening is favored by the acidic phenolic function, thus closing into the more stable six-membered ring compound. We confirmed the hypothesized reaction mechanism, by applying the same reaction conditions while starting from the corresponding methyl ketone. This undesired compound, easily and quantitatively obtained by standard Johnson-Corey-Chaykovsky conditions, could pave the way to a new methodology for the obtainment of 2,3-disubstituted 1,4-naphthodioxanes, further derivatizable.

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