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Special Issue "Organometallic Catalysis in Organic Synthesis"

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

Deadline for manuscript submissions: 28 August 2018

Special Issue Editors

Guest Editor
Prof. Dr. Albert Demonceau

Department of Chemistry, University of Liège, Sart-Tilman (B.6a), 4000 Liège, Belgium
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Interests: macromolecular chemistry; organometallic synthesis; homogeneous catalysis; carbon-carbon bond formation; ruthenium-arene complexes
Guest Editor
Prof. Dr. Ileana Dragutan

Institute of Organic Chemistry of the Romanian Academy, 202B Spl. Independentei, 060023 Bucharest, P.O. Box 35-108, Romania
E-Mail
Interests: transition metals complexes and their chemistry and use in homogeneous catalysis and polymer synthesis; Ru-catalyzed olefin metathesis; metathesis driven syntheses of some bioactive compounds and metathesis-related processes; stable nitroxide free radicals and their preparation and multifarious applications using ESR
Guest Editor
Prof. Dr. Valerian Dragutan

Institute of Organic Chemistry of the Romanian Academy, 202B Spl. Independentei, 060023 Bucharest, P.O. Box 35-108, Romania
E-Mail
Phone: +4021-316-79.00
Interests: organic synthesis; natural compounds; heterocyclic compounds; reactive organometallic and coordination compounds; bioactive organotin; transition metal complexes; asymmetric catalysis; stereoselective Ziegler-Natta polymerization; organometallic polymers

Special Issue Information

Dear Colleagues,

Catalysis by organometallics is currently of utmost significance in important industries, such as the manufacture of advanced materials, pharmaceuticals, or biomaterials, in petrochemistry, nanotechnology, and in emerging technologies of smart products, catalytic water oxidation, high-tech energy saving, etc. Therefore, this Special Issue aims to illustrate the most recent and pertinent developments on the multiple, innovative uses of organometallics as effective homogeneous and heterogeneous catalysts in a plethora of organic syntheses. Organized, so as to cover new applications of organometallics where metals pertain to the main groups, transition metals or rare earth metals, the contributions will focus on a broad range of organic reactions, such as C-H activation, C-C bond formation, addition, condensation, metathesis, isomerization, oligomerization, hydrogenation and hydrogen transfer, oxidation, epoxidation, hydration, hydroboration, hydrosilylation, hydroxylation, hydroformylation, carbonylation, cyclopropanation, cyclization and related reactions, as well as on their involvement in the synthesis of polycyclic compounds or bioactive natural products. Special attention will be paid to complex catalytic processes, occurring in solution and solid phase, and to tandem or cascade reactions implying organometallics. The key role of the transient organometallic species intervening in the catalytic cycles will also be highlighted.

Communications, full papers and reviews on the abovementioned topics are particularly welcome.

Prof. Dr. Albert Demonceau
Prof. Dr. Ileana Dragutan
Prof. Dr. Valerian Dragutan
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 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

  • homogeneous catalysis
  • heterogeneous catalysis
  • new synthetic methods
  • enantioselective synthesis
  • organic synthesis
  • green chemistry
  • energy saving
  • sustainable development
  • physical methods
  • computational chemistry
  • mechanistic studies
  • industrial applications

Published Papers (7 papers)

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Research

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Open AccessArticle Development of Conjugate Addition of Lithium Dialkylcuprates to Thiochromones: Synthesis of 2-Alkylthiochroman-4-ones and Additional Synthetic Applications
Molecules 2018, 23(7), 1728; https://doi.org/10.3390/molecules23071728
Received: 16 June 2018 / Revised: 5 July 2018 / Accepted: 13 July 2018 / Published: 15 July 2018
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Abstract
Lithium dialkylcuprates undergo conjugate addition to thiochromones to afford 2-alkylthiochroman-4-ones in good yields. This approach provide an efficient and general synthetic approach to privileged sulfur-containing structural motifs and valuable precursors for many pharmaceuticals, starting from common substrates-thiochromones. Good yields of 2-alkyl-substituted thiochroman-4-ones are
[...] Read more.
Lithium dialkylcuprates undergo conjugate addition to thiochromones to afford 2-alkylthiochroman-4-ones in good yields. This approach provide an efficient and general synthetic approach to privileged sulfur-containing structural motifs and valuable precursors for many pharmaceuticals, starting from common substrates-thiochromones. Good yields of 2-alkyl-substituted thiochroman-4-ones are attained with lithium dialkylcuprates, lithium alkylcyanocuprates or substoichiometric amount of copper salts. The use of commercially available inexpensive alkyllithium reagents will expedite the synthesis of a large library of 2-alkyl substituted thiochroman-4-ones for additional synthetic applications. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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Open AccessArticle High Conversion of Styrene, Ethylene, and Hydrogen to Linear Monoalkylbenzenes
Molecules 2018, 23(6), 1260; https://doi.org/10.3390/molecules23061260
Received: 30 March 2018 / Revised: 21 May 2018 / Accepted: 23 May 2018 / Published: 25 May 2018
PDF Full-text (2040 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
1-Alkylbenzenes as a precursor of surfactants, can be produced from ethylene, styrene, and hydrogen. These intermediates, lacking tertiary carbons, are environmentally more benign than commercial ones that bear the aromatic ring linked to an internal carbon of the aliphatic chain. The one-pot synthesis
[...] Read more.
1-Alkylbenzenes as a precursor of surfactants, can be produced from ethylene, styrene, and hydrogen. These intermediates, lacking tertiary carbons, are environmentally more benign than commercial ones that bear the aromatic ring linked to an internal carbon of the aliphatic chain. The one-pot synthesis of highly linear 1-alkylbenzenes (LABs) through the homogeneous catalysis of olefin poly-insertion from cheap and largely available reagents can be carried out with a high turnover and selectivity. A purposely designed reactor that allows for the fine control of the three components feed, along with temperature, plays a key role in this achievement. A turnover of 194 g of LABs per mmol of catalyst per hour can be obtained with the simultaneous removal of polyethylene as a by-product. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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Open AccessArticle Poly(urethane-norbornene) Aerogels via Ring Opening Metathesis Polymerization of Dendritic Urethane-Norbornene Monomers: Structure-Property Relationships as a Function of an Aliphatic Versus an Aromatic Core and the Number of Peripheral Norbornene Moieties
Molecules 2018, 23(5), 1007; https://doi.org/10.3390/molecules23051007
Received: 2 March 2018 / Revised: 13 April 2018 / Accepted: 21 April 2018 / Published: 25 April 2018
Cited by 1 | PDF Full-text (5795 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
We report the synthesis and characterization of synthetic polymer aerogels based on dendritic-type urethane-norbornene monomers. The core of those monomers is based either on an aromatic/rigid (TIPM/Desmodur RE), or an aliphatic/flexible (Desmodur N3300) triisocyanate. The terminal norbornene groups (three at the tip of
[...] Read more.
We report the synthesis and characterization of synthetic polymer aerogels based on dendritic-type urethane-norbornene monomers. The core of those monomers is based either on an aromatic/rigid (TIPM/Desmodur RE), or an aliphatic/flexible (Desmodur N3300) triisocyanate. The terminal norbornene groups (three at the tip of each of the three branches) were polymerized via ROMP using the inexpensive 1st generation Grubbs catalyst. The polymerization/gelation conditions were optimized by varying the amount of the catalyst. The resulting wet-gels were dried either from pentane under ambient pressure at 50 °C, or from t-butanol via freeze-drying, or by using supercritical fluid (SCF) CO2. Monomers were characterized with high resolution mass spectrometry (HRMS), 1H- and solid-state 13C-NMR. Aerogels were characterized with ATR-FTIR and solid-state 13C-NMR. The porous network was probed with N2-sorption and SEM. The thermal stability of monomers and aerogels was studied with TGA, which also provides evidence for the number of norbornene groups that reacted via ROMP. At low densities (<0.1 g cm−3) all aerogels were highly porous (porosity > 90%), mostly macroporous materials; aerogels based on the aliphatic/flexible core were fragile, whereas aerogels containing the aromatic/rigid core were plastic, and at even lower densities (0.03 g cm−3) foamy. At higher densities (0.2–0.7 g cm−3) all materials were stiff, strong, and hard. At low monomer concentrations all aerogels consisted of discrete primary particles that formed spherical secondary aggregates. At higher monomer concentrations the structure consisted of fused particles with the size of the previous secondary aggregates, due to the low solubility of the developing polymer, which phase-separated and formed a primary particle network. Same-size fused aggregates were observed for both aliphatic and aromatic triisocyanate-derived aerogels, leading to the conclusion that it is not the aliphatic or aromatic core that determines phase separation, but rather the solubility of the polymeric backbone (polynorbornene) that is in both cases the same. The material properties were compared to those of analogous aerogels bearing only one norbornene moiety at the tip of each branch deriving from the same cores. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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Open AccessArticle Ruthenium(η61-arene-CH2-NHC) Catalysts for Direct Arylation of 2-Phenylpyridine with (Hetero)Aryl Chlorides in Water
Molecules 2018, 23(3), 647; https://doi.org/10.3390/molecules23030647
Received: 16 February 2018 / Revised: 7 March 2018 / Accepted: 7 March 2018 / Published: 13 March 2018
Cited by 3 | PDF Full-text (2591 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A series of new benzimidazolium halides were synthesized in good yields as unsymmetrical N-heterocyclic carbene (NHC) precursors containing the N–CH2–arene group. The benzimidazolium halides were readily converted into ruthenium(II)–NHC complexes with the general formula [RuCl261
[...] Read more.
A series of new benzimidazolium halides were synthesized in good yields as unsymmetrical N-heterocyclic carbene (NHC) precursors containing the N–CH2–arene group. The benzimidazolium halides were readily converted into ruthenium(II)–NHC complexes with the general formula [RuCl261–arene–CH2–NHC)]. The structures of all new compounds were characterized by 1H NMR (Nuclear Magnetic Resonance), 13C NMR, FT-IR (Fourier Transform Infrared) spectroscopy and elemental analysis techniques. The single crystal structure of one benzimidazole ruthenium complex, 2b, was determined. The complex is best thought of as containing an octahedrally coordinated Ru center with the arene residue occupying three sites, the remaining sites being occupied by a (carbene)C–Ru bond and two Ru–Cl bonds. The catalytic activity of [RuCl261–arene–CH2–NHC)] complexes was evaluated in the direct (hetero)arylation of 2-phenylpyridine with (hetero)aryl chlorides in water as the nontoxic reaction medium. These results show that catalysts 2a and 2b were the best for monoarylation with simple phenyl and tolyl chlorides. For functional aryl chlorides, 2d, 2e, and 2c appeared to be the most efficient. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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Open AccessArticle Gold-Catalyzed Addition of β-Ketoesters to Alkenes: Influence of Electronic and Steric Effects in the Reaction Outcome
Molecules 2018, 23(3), 629; https://doi.org/10.3390/molecules23030629
Received: 7 February 2018 / Revised: 27 February 2018 / Accepted: 9 March 2018 / Published: 10 March 2018
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Abstract
The gold-catalyzed intermolecular hydroalkylation of olefins with β-ketoesters represents a conceptually attractive and useful synthetic tool; however, it has been scarcely applied, remaining a challenge for chemists. The aim of the current study was to investigate the addition of these 1,3-diketo-compounds to alkenes
[...] Read more.
The gold-catalyzed intermolecular hydroalkylation of olefins with β-ketoesters represents a conceptually attractive and useful synthetic tool; however, it has been scarcely applied, remaining a challenge for chemists. The aim of the current study was to investigate the addition of these 1,3-diketo-compounds to alkenes under gold catalysis conditions, in order to establish the electronic and steric effects of the alkenyl substrates in the reaction outcome. The screening of different catalyst systems and diverse olefins enabled defining the alkenyl requirements and the best reaction conditions to efficiently achieve the coupled products. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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Open AccessArticle Platinum-Catalyzed Allylation of 2,3-Disubstituted Indoles with Allylic Acetates
Molecules 2017, 22(12), 2097; https://doi.org/10.3390/molecules22122097
Received: 20 October 2017 / Revised: 24 November 2017 / Accepted: 28 November 2017 / Published: 29 November 2017
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Abstract
Given the importance of heterocycle indole derivatives, much effort has been directed toward the development of methods for functionalization of the indole nucleus at N1 and C3 sites. Moreover, the platinum-catalyzed allyation of nucleophiles was an established and efficient way, which has been
[...] Read more.
Given the importance of heterocycle indole derivatives, much effort has been directed toward the development of methods for functionalization of the indole nucleus at N1 and C3 sites. Moreover, the platinum-catalyzed allyation of nucleophiles was an established and efficient way, which has been applied to medicinal and organic chemistry. In our research, the platinum-catalyzed 2,3-disubstitued indoles with allylic acetates was investigated under different conditions. Herein, we established a simple, convenient, and efficient method, which afforded high yield of allylated indoles. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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Review

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Open AccessFeature PaperReview Synthesis and Application of the Transition Metal Complexes of α-Pyridinyl Alcohols, α-Bipyridinyl Alcohols, α,α’-Pyridinyl Diols and α,α’-Bipyridinyl Diols in Homogeneous Catalysis
Molecules 2018, 23(4), 896; https://doi.org/10.3390/molecules23040896
Received: 28 February 2018 / Revised: 6 April 2018 / Accepted: 6 April 2018 / Published: 12 April 2018
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Abstract
The paper presents a comprehensive survey on the synthetic procedures of transition metal complexes of α-pyridinyl alcoholato, α-bipyridinyl alcoholato, α,α’-pyridinyl dialcoholato and α,α’-bipyridinyl dialcoholato ligands and their coordination chemistry. Greater emphasis is, however, given to the catalytic activity of the complexes
[...] Read more.
The paper presents a comprehensive survey on the synthetic procedures of transition metal complexes of α-pyridinyl alcoholato, α-bipyridinyl alcoholato, α,α’-pyridinyl dialcoholato and α,α’-bipyridinyl dialcoholato ligands and their coordination chemistry. Greater emphasis is, however, given to the catalytic activity of the complexes in homogeneous and asymmetric chemical reactions. The multidentate character of the pyridinyl alcohols and/or bipyridinyl diols is of great importance in the complexation with a large number and type of transition metals. The transition metal complexes of pyridinyl alcoholato or bipyridinyl dialcoholato ligands in most cases, and a few pyridinyl alcohols alone, were used as catalysts in homogeneous and chemical asymmetric reactions. In most of the homogeneously catalysed enantioselective chemical reactions, limited numbers and types of pyridinyl alcohols and or bipyridinyl diols were used in the preparation of chiral catalysts that led to a few investigations on the catalytic importance of the pyridinyl alcohols. Full article
(This article belongs to the Special Issue Organometallic Catalysis in Organic Synthesis)
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