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Special Issue "Recent Synthetic Aspects on the Chemistry of Nitro, Nitroso and Amino Compounds"

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

Deadline for manuscript submissions: closed (10 June 2016)

Special Issue Editor

Guest Editor
Prof. Dr. Alessandro Palmieri

Green Chemistry Group, School of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino (MC), Italy
Website | E-Mail
Interests: green chemistry; nitro compounds; flow chemistry; one-pot processes; heterocycle synthesis

Special Issue Information

Dear Colleagues,

Nitrogen-containing molecules are largely present in our daily life, being at very core of many substances acting as pharmeceuticals, fertilizers, explosives, proteins, etc. Among them, nitro, nitroso, and amino derivatives, thanks to their great chemical versatility, play a prominent role in synthesis and are largely investigated as precursors of highly functionalized materials, and as catalysts or ligands, respectively, in organo- and metal-catalyzed processes. Each class of these derivatives is featured by a different oxidation state of the nitrogen atom, which, in principle, would enable their interconversion through a redox process. The nitrogen atom can be easily inserted into organic molecules in its higher oxidation state as a nitro group from which nitroso or amino derivatives can be obtained by a reductive process. On the other hand, modern synthetic methods allow a direct introduction of the amino moiety through reductive or electrophilic amination.

With this Special Issue, we intend to highlight the latest important results concerning the chemistry of these key derivatives, discussing new emerging protocols for their preparation and their applications for new carbon-carbon (C–C) and carbon-heteroatom (C–X) bond formation.

Prof. Dr. Alessandro Palmieri
Guest Editor

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 papers will be 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 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 1800 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

  • nitro compounds
  • nitroso compounds
  • amines
  • heterocycles
  • carbon–carbon bond formation
  • carbon–heteroatom bond formation

Published Papers (8 papers)

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Editorial

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Open AccessEditorial Special Issue “Recent Synthetic Aspects on the Chemistry of Nitro, Nitroso and Amino Compounds”
Molecules 2017, 22(1), 9; doi:10.3390/molecules22010009
Received: 20 December 2016 / Accepted: 21 December 2016 / Published: 23 December 2016
PDF Full-text (144 KB) | HTML Full-text | XML Full-text
Abstract
Nitrogen-containing molecules are key scaffolds that are widely applied in organic synthesis as precursors of highly functionalized materials, and are also investigated for their biological activities. This Special Issue collects seven innovative contributions which expand our knowledge of the chemistry of nitro compounds,
[...] Read more.
Nitrogen-containing molecules are key scaffolds that are widely applied in organic synthesis as precursors of highly functionalized materials, and are also investigated for their biological activities. This Special Issue collects seven innovative contributions which expand our knowledge of the chemistry of nitro compounds, amines, diazonium salts, and peptides, and that provide a good overview about their main reactivities. Full article

Research

Jump to: Editorial

Open AccessArticle A General Catalytic Enantioselective Transfer Hydrogenation Reaction of β,β-Disubstituted Nitroalkenes Promoted by a Simple Organocatalyst
Molecules 2016, 21(8), 1000; doi:10.3390/molecules21081000
Received: 28 June 2016 / Revised: 15 July 2016 / Accepted: 28 July 2016 / Published: 30 July 2016
Cited by 3 | PDF Full-text (3675 KB) | HTML Full-text | XML Full-text
Abstract
Given its synthetic relevance, the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes has received a great deal of attention. Several bio-, metal-, and organo-catalytic methods have been developed, which however are usually applicable to single classes of nitroalkene substrates. In this paper, we present
[...] Read more.
Given its synthetic relevance, the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes has received a great deal of attention. Several bio-, metal-, and organo-catalytic methods have been developed, which however are usually applicable to single classes of nitroalkene substrates. In this paper, we present an account of our previous work on this transformation, which implemented with new disclosures and mechanistic insights results in a very general protocol for nitroalkene reductions. The proposed methodology is characterized by (i) a remarkably broad scope encompassing various nitroalkene classes; (ii) Hantzsch esters as convenient (on a preparative scale) hydrogen surrogates; (iii) a simple and commercially available thiourea as catalyst; (iv) user-friendly procedures. Overall, the proposed protocol gives a practical dimension to the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes, offering a useful and general platform for the preparation of nitroalkanes bearing a stereogenic center at the β-position in a highly enantioenriched form. A transition state model derived from control kinetic experiments combined with literature data is proposed and discussed. This model accounts and justifies the observed experimental results. Full article
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Open AccessArticle Exploring Flow Procedures for Diazonium Formation
Molecules 2016, 21(7), 918; doi:10.3390/molecules21070918
Received: 12 June 2016 / Revised: 29 June 2016 / Accepted: 5 July 2016 / Published: 14 July 2016
Cited by 4 | PDF Full-text (1744 KB) | HTML Full-text | XML Full-text
Abstract
The synthesis of diazonium salts is historically an important transformation extensively utilized in dye manufacture. However the highly reactive nature of the diazonium functionality has additionally led to the development of many new reactions including several carbon-carbon bond forming processes. It is therefore
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The synthesis of diazonium salts is historically an important transformation extensively utilized in dye manufacture. However the highly reactive nature of the diazonium functionality has additionally led to the development of many new reactions including several carbon-carbon bond forming processes. It is therefore highly desirable to determine optimum conditions for the formation of diazonium compounds utilizing the latest processing tools such as flow chemistry to take advantage of the increased safety and continuous manufacturing capabilities. Herein we report a series of flow-based procedures to prepare diazonium salts for subsequent in-situ consumption. Full article
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Open AccessArticle Aza-Michael Mono-addition Using Acidic Alumina under Solventless Conditions
Molecules 2016, 21(6), 815; doi:10.3390/molecules21060815
Received: 20 May 2016 / Revised: 10 June 2016 / Accepted: 16 June 2016 / Published: 22 June 2016
Cited by 3 | PDF Full-text (1284 KB) | HTML Full-text | XML Full-text
Abstract
Aza-Michael reactions between primary aliphatic and aromatic amines and various Michael acceptors have been performed under environmentally-friendly solventless conditions using acidic alumina as a heterogeneous catalyst to selectively obtain the corresponding mono-adducts in high yields. Ethyl acrylate was the main acceptor used, although
[...] Read more.
Aza-Michael reactions between primary aliphatic and aromatic amines and various Michael acceptors have been performed under environmentally-friendly solventless conditions using acidic alumina as a heterogeneous catalyst to selectively obtain the corresponding mono-adducts in high yields. Ethyl acrylate was the main acceptor used, although others such as acrylonitrile, methyl acrylate and acrylamide were also utilized successfully. Bi-functional amines also gave the mono-adducts in good to excellent yields. Such compounds can serve as intermediates for the synthesis of anti-cancer and antibiotic drugs. Full article
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Open AccessCommunication A New One-Pot Synthesis of Quinoline-2-carboxylates under Heterogeneous Conditions
Molecules 2016, 21(6), 776; doi:10.3390/molecules21060776
Received: 24 May 2016 / Revised: 7 June 2016 / Accepted: 8 June 2016 / Published: 15 June 2016
Cited by 2 | PDF Full-text (1267 KB) | HTML Full-text | XML Full-text
Abstract
Quinoline-2-carboxylates are an important subclass of quinoline derivatives largely present in a variety of biologically active molecules, as well as useful ligands in metal-catalyzed reactions. Herein, we present a new one-pot protocol for synthesizing this class of derivatives starting from β-nitroacrylates and 2-aminobenzaldehydes.
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Quinoline-2-carboxylates are an important subclass of quinoline derivatives largely present in a variety of biologically active molecules, as well as useful ligands in metal-catalyzed reactions. Herein, we present a new one-pot protocol for synthesizing this class of derivatives starting from β-nitroacrylates and 2-aminobenzaldehydes. In order to optimize the protocol, we investigated several reaction conditions, obtaining the best results using the 2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) as solid base, in acetonitrile. Finally, we demonstrated the generality of our approach over several substrates which led to synthesize a plethora of functionalized quinolines-2-carboxylate derivatives in good overall yields. Full article
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Open AccessArticle Solid Phase Formylation of N-Terminus Peptides
Molecules 2016, 21(6), 736; doi:10.3390/molecules21060736
Received: 26 April 2016 / Revised: 27 May 2016 / Accepted: 1 June 2016 / Published: 4 June 2016
Cited by 5 | PDF Full-text (1030 KB) | HTML Full-text | XML Full-text
Abstract
Formylation of amino groups is a critical reaction involved in several biological processes including post-translational modification of histones. The addition of a formyl group (CHO) to the N-terminal end of a peptide chain generates biologically active molecules. N-formyl-peptides can be produced by different
[...] Read more.
Formylation of amino groups is a critical reaction involved in several biological processes including post-translational modification of histones. The addition of a formyl group (CHO) to the N-terminal end of a peptide chain generates biologically active molecules. N-formyl-peptides can be produced by different methods. We performed the N-formylation of two chemotactic hexapetides, Met1-Leu2-Lys3-Leu4-Ile5-Val6 and Met1-Met2-Tyr3-Ala4-Leu5-Phe6, carrying out the reaction directly on peptidyl-resin following pre-activation of formic acid with N,N-dicyclohexylcarbodiimmide (DCC) in liquid phase. The overnight incubation at 4 °C resulted in a significant increase in production yields of formylated peptides compared to the reaction performed at room temperature. The method is consistently effective, rapid, and inexpensive. Moreover, the synthetic strategy can be applied for the formylation of all primary amines at N-terminus of peptide chains or amino groups of lysine side-chains in solid phase. Full article
Open AccessArticle Aza-Henry Reactions on C-Alkyl Substituted Aldimines
Molecules 2016, 21(6), 723; doi:10.3390/molecules21060723
Received: 3 May 2016 / Revised: 26 May 2016 / Accepted: 26 May 2016 / Published: 2 June 2016
Cited by 4 | PDF Full-text (2242 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The reactivity of C-CH3 substituted N-protected aldimines in aza-Henry addition reactions was compared with that of the analogous trifluoromethylated compounds. C-Alkyl aldimines easily reacted with nitro alkanes under solvent-free conditions and in the absence of catalyst, despite being worse
[...] Read more.
The reactivity of C-CH3 substituted N-protected aldimines in aza-Henry addition reactions was compared with that of the analogous trifluoromethylated compounds. C-Alkyl aldimines easily reacted with nitro alkanes under solvent-free conditions and in the absence of catalyst, despite being worse electrophiles than C-CF3 aldimines, they gave the aza-Henry addition only when ZrCl4 was added. The presence of a bulky group on the imine carbon deeply influenced the reactivity. Full article
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Open AccessArticle Synthesis of Novel Quaternary Ammonium Salts and Their in Vitro Antileishmanial Activity and U-937 Cell Cytotoxicity
Molecules 2016, 21(4), 381; doi:10.3390/molecules21040381
Received: 25 February 2016 / Revised: 11 March 2016 / Accepted: 14 March 2016 / Published: 29 March 2016
Cited by 2 | PDF Full-text (992 KB) | HTML Full-text | XML Full-text
Abstract
This work describes the synthesis of a series of quaternary ammonium salts and the assessment of their in vitro antileishmanial activity and cytotoxicity. A preliminary discussion on a structure-activity relationship of the compounds is also included. Three series of quaternary ammonium salts were
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This work describes the synthesis of a series of quaternary ammonium salts and the assessment of their in vitro antileishmanial activity and cytotoxicity. A preliminary discussion on a structure-activity relationship of the compounds is also included. Three series of quaternary ammonium salts were prepared: (i) halomethylated quaternary ammonium salts (series I); (ii) non-halogenated quaternary ammonium salts (series II) and (iii) halomethylated choline analogs (series III). Assessments of their in vitro cytotoxicity in human promonocytic cells U-937 and antileishmanial activity in axenic amastigotes of L. (Viannia) panamensis (M/HOM/87/UA140-pIR-eGFP) were carried out using the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide) micromethod. Antileishmanial activity was also tested in intracellular amastigotes of L. (V) panamensis using flow cytometry. High toxicity for human U937 cells was found with most of the compounds, which exhibited Lethal Concentration 50 (LC50) values in the range of 9 to 46 μg/mL. Most of the compounds evidenced antileishmanial activity. In axenic amastigotes, the antileishmanial activity varied from 14 to 57 μg/mL, while in intracellular amastigotes their activity varied from 17 to 50 μg/mL. N-Chloromethyl-N,N-dimethyl-N-(4,4-diphenylbut-3-en-1-yl)ammonium iodide (1a), N-iodomethyl-N,N-dimethyl-N-(4,4-diphenylbut-3-en-1-yl)ammonium iodide (2a), N,N,N-trimethyl-N-(4,4-diphenylbut-3-en-1-yl)ammonium iodide (3a) and N,N,N-trimethyl-N-(5,5-diphenylpent-4-en-1-yl)ammonium iodide (3b) turned out to be the most active compounds against intracellular amastigotes of L. (V) panamensis, with EC50 values varying between 24.7 for compound 3b and 38.4 μg/mL for compound 1a. Thus, these compounds represents new “hits” in the development of leishmanicidal drugs. Full article
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