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Reactions of Hydrocarbons and other C‒H Compounds
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Reactions of Hydrocarbons and other C‒H Compounds

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

Deadline for manuscript submissions: closed (10 December 2016) | Viewed by 46049

Special Issue Editor

Prof. Dr. Georgiy B. Shul'pin

E-Mail Website
Guest Editor
Russian Academy of Sciences, Semenov Institute of Chemical Physics, Moscow, Russia
Interests: metal complex catalysis; biomimetic catalysis; photocatalysis; oxidation of hydrocarbons; catalytic activation and functionalization of C–H bonds in hydrocarbons; organometallic chemistry; regioselectivity
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

One of the most important processes for organic chemistry, as well as for the chemical and petroleum industry, is breaking bonds C–H and C–C in various compounds, and primarily, in hydrocarbons. Among hydrocarbons, saturated hydrocarbons (alkanes) are especially attractive as substrates for chemical transformations. However, these substances are known to be the less reactive organic compounds. In the last decades, new reactions of hydrocarbons under mild conditions have been discovered. For example, these reactions include alkane transformations in superacid media, interactions with metal atoms and ions, and interactions with radicals and carbenes. The development of coordination metal-complex catalysis led to the discovery of the ability of various types of molecules, including molecular hydrogen, carbon monoxide, oxygen, nitrogen, olefins, acetylenes, aromatic compounds, to take part in various reactions in homogeneous solutions. New catalytic systems based on metal complexes have been discovered, which allow us to introduce various groups into hydrocarbons, as well as other C–H compounds. See, for example: A. E. Shilov, G. B. Shul’pin, “Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes”, Kluwer, New York, Boston, Dordrecht, London, Moscow, 2002; G. B. Shul’pin, “C–H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst’s activity and selectivity”, Perspective, Dalton Trans., 2013, 42, 12794–12818; G. B. Shul’pin, “New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review”, Catalysts, 2016, 6, 50.

Papers which describe various transformations of saturated, aromatic, olefinic hydrocarbons, as well as alcohols, ketones accompanied by the C–H and C–C bond splitting will be presented in this Special Issue. Theoretical investigations and DFT calculations, are welcome. Full comprehensive reviews and mini-reviews, covering various fields of catalytic and non-catalytic transformations describing new unusual catalysts, new unusual solvents, new methods of inducing reactions (by irradiation, etc.) will be very helpful for the reader.

Prof. Georgiy B. Shul’pin
Guest Editor

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Keywords

  • hydrocarbons
  • alkanes
  • olefins
  • aromatics
  • C–H functionlization
  • alcohols
  • ketones
  • carboxylic acids
  • alkyl peroxides
  • hydrogen peroxides
  • oxidation
  • oxygenation
  • isomerization
  • craking
  • hydrogenation
  • gehydrogenation
  • reaction kinetics
  • reaction mechanism
  • green chemistry
  • homogeneous catalysis
  • heterogeneous catalysis
  • selectivity
  • enzymatic transformations
  • petroleum industry
  • gas-phase reactions

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Published Papers (6 papers)

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Research

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3225 KiB  
Article
Gold Nanoparticles Deposited on Surface Modified Carbon Xerogels as Reusable Catalysts for Cyclohexane C-H Activation in the Presence of CO and Water
by Ana Paula da Costa Ribeiro, Luísa Margarida Dias Ribeiro de Sousa Martins, Sónia Alexandra Correia Carabineiro, José Luís Figueiredo and Armando José Latourrette Pombeiro
Molecules 2017, 22(4), 603; https://doi.org/10.3390/molecules22040603 - 9 Apr 2017
Cited by 21 | Viewed by 5383
Abstract
The use of gold as a promotor of alkane hydrocarboxylation is reported for the first time. Cyclohexane hydrocarboxylation to cyclohexanecarboxylic acid (up to 55% yield) with CO, water, and peroxodisulfate in a water/acetonitrile medium at circa 50 °C has been achieved in the [...] Read more.
The use of gold as a promotor of alkane hydrocarboxylation is reported for the first time. Cyclohexane hydrocarboxylation to cyclohexanecarboxylic acid (up to 55% yield) with CO, water, and peroxodisulfate in a water/acetonitrile medium at circa 50 °C has been achieved in the presence of gold nanoparticles deposited by a colloidal method on a carbon xerogel in its original form (CX), after oxidation with HNO3 (-ox), or after oxidation with HNO3 and subsequent treatment with NaOH (-ox-Na). Au/CX-ox-Na behaves as re-usable catalyst maintaining its initial activity and selectivity for at least seven consecutive cycles. Green metric values of atom economy or carbon efficiency also attest to the improvement brought by this novel catalytic system to the hydrocarboxylation of cyclohexane. Full article
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)
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1883 KiB  
Article
Metal-Free α-C(sp3)–H Functionalized Oxidative Cyclization of Tertiary N,N-Diaryl Amino Alcohols: Theoretical Approach for Mechanistic Pathway
by Zakir Ullah and Mihyun Kim
Molecules 2017, 22(4), 547; https://doi.org/10.3390/molecules22040547 - 29 Mar 2017
Cited by 9 | Viewed by 6942
Abstract
The mechanistic pathway of TEMPO/I2-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 was investigated. Based on direct empirical experiments, three key intermediates (aminium radical cation 3, α-aminoalkyl radical 4, and iminium 5), four types of reactive species [...] Read more.
The mechanistic pathway of TEMPO/I2-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 was investigated. Based on direct empirical experiments, three key intermediates (aminium radical cation 3, α-aminoalkyl radical 4, and iminium 5), four types of reactive species (radical TEMPO, cationic TEMPO, TEMPO-I, and iodo radical), and three types of pathways ((1) SET/PCET mechanism; (2) HAT/1,6-H transfer mechanism; (3) ionic mechanism) were assumed. Under the assumption, nine free energy diagrams were acquired through density functional theory calculations. From the comparison of solution-phase free energy, some possible mechanisms were excluded, and then the chosen plausible mechanisms were concretized using the more stable intermediate 7. Full article
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)
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Figure 1

1889 KiB  
Communication
Atom-Economic Synthesis of 4-Pyrones from Diynones and Water
by Yan-Li Xu, Qing-Hu Teng, Wei Tong, Heng-Shan Wang, Ying-Ming Pan and Xian-Li Ma
Molecules 2017, 22(1), 109; https://doi.org/10.3390/molecules22010109 - 10 Jan 2017
Cited by 22 | Viewed by 7732
Abstract
Transition-metal-free synthesis of 4-pyrones via TfOH-promoted nucleophilic addition/cyclization of diynones and water has been developed. This transformation is simple, atom economical and environmentally benign, providing rapid and efficient access to substituted 4-pyrones. Full article
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)
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2808 KiB  
Article
Stereoselective Alkane Oxidation with meta-Chloroperoxybenzoic Acid (MCPBA) Catalyzed by Organometallic Cobalt Complexes
by Georgiy B. Shul’pin, Dmitriy A. Loginov, Lidia S. Shul’pina, Nikolay S. Ikonnikov, Vladislav O. Idrisov, Mikhail M. Vinogradov, Sergey N. Osipov, Yulia V. Nelyubina and Polina M. Tyubaeva
Molecules 2016, 21(11), 1593; https://doi.org/10.3390/molecules21111593 - 22 Nov 2016
Cited by 29 | Viewed by 10228
Abstract
Cobalt pi-complexes, previously described in the literature and specially synthesized and characterized in this work, were used as catalysts in homogeneous oxidation of organic compounds with peroxides. These complexes contain pi-butadienyl and pi-cyclopentadienyl ligands: [(tetramethylcyclobutadiene)(benzene)cobalt] hexafluorophosphate, [(C4Me4)Co(C6H [...] Read more.
Cobalt pi-complexes, previously described in the literature and specially synthesized and characterized in this work, were used as catalysts in homogeneous oxidation of organic compounds with peroxides. These complexes contain pi-butadienyl and pi-cyclopentadienyl ligands: [(tetramethylcyclobutadiene)(benzene)cobalt] hexafluorophosphate, [(C4Me4)Co(C6H6)]PF6 (1); diiodo(carbonyl)(pentamethylcyclopentadienyl)cobalt, Cp*Co(CO)I2 (2); diiodo(carbonyl)(cyclopentadienyl)cobalt, CpCo(CO)I2 (3); (tetramethylcyclobutadiene)(dicarbonyl)(iodo)cobalt, (C4Me4)Co(CO)2I (4); [(tetramethylcyclobutadiene)(acetonitrile)(2,2′-bipyridyl)cobalt] hexafluorophosphate, [(C4Me4)Co(bipy)(MeCN)]PF6 (5); bis[dicarbonyl(B-cyclohexylborole)]cobalt, [(C4H4BCy)Co(CO)2]2 (6); [(pentamethylcyclopentadienyl)(iodo)(1,10-phenanthroline)cobalt] hexafluorophosphate, [Cp*Co(phen)I]PF6 (7); diiodo(cyclopentadienyl)cobalt, [CpCoI2]2 (8); [(cyclopentadienyl)(iodo)(2,2′-bipyridyl)cobalt] hexafluorophosphate, [CpCo(bipy)I]PF6 (9); and [(pentamethylcyclopentadienyl)(iodo)(2,2′-bipyridyl)cobalt] hexafluorophosphate, [Cp*Co(bipy)I]PF6 (10). Complexes 1 and 2 catalyze very efficient and stereoselective oxygenation of tertiary C–H bonds in isomeric dimethylcyclohexanes with MCBA: cyclohexanols are produced in 39 and 53% yields and with the trans/cis ratio (of isomers with mutual trans- or cis-configuration of two methyl groups) 0.05 and 0.06, respectively. Addition of nitric acid as co-catalyst dramatically enhances both the yield of oxygenates and stereoselectivity parameter. In contrast to compounds 1 and 2, complexes 9 and 10 turned out to be very poor catalysts (the yields of oxygenates in the reaction with cis-1,2-dimethylcyclohexane were only 5%–7% and trans/cis ratio 0.8 indicated that the oxidation is not stereoselective). The chromatograms of the reaction mixture obtained before and after reduction with PPh3 are very similar, which testifies that alkyl hydroperoxides are not formed in this oxidation. It can be thus concluded that the interaction of the alkanes with MCPBA occurs without the formation of free radicals. The complexes catalyze oxidation of alcohols with tert-butylhydroperoxide (TBHP). For example, tert-BuOOH efficiently oxidizes 1-phenylethanol to acetophenone in 98% yield if compound 1 is used as a catalyst. Full article
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)
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457 KiB  
Communication
Palladium-Catalyzed C–H Arylation of 1,2,3-Triazoles
by Chengwei Zhang, Lin You and Chuo Chen
Molecules 2016, 21(10), 1268; https://doi.org/10.3390/molecules21101268 - 22 Sep 2016
Cited by 7 | Viewed by 4989
Abstract
Palladium(II) acetate, in combination with triphenylphosphine, catalyzes direct arylation of 1,4-disubstituted 1,2,3-triazoles effectively. This C–H arylation reaction provides facile access to fully substituted triazoles with well-defined regiochemistry. Full article
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)

Review

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1806 KiB  
Review
Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts
by Roman V. Ottenbacher, Evgenii P. Talsi and Konstantin P. Bryliakov
Molecules 2016, 21(11), 1454; https://doi.org/10.3390/molecules21111454 - 31 Oct 2016
Cited by 34 | Viewed by 8391
Abstract
Non-heme iron(II) complexes are widespread synthetic enzyme models, capable of conducting selective C–H oxidation with H2O2 in the presence of carboxylic acid additives. In the last years, structurally similar manganese(II) complexes have been shown to catalyze C–H oxidation with similarly [...] Read more.
Non-heme iron(II) complexes are widespread synthetic enzyme models, capable of conducting selective C–H oxidation with H2O2 in the presence of carboxylic acid additives. In the last years, structurally similar manganese(II) complexes have been shown to catalyze C–H oxidation with similarly high selectivity, and with much higher efficiency. In this mini-review, recent catalytic and mechanistic data on the selective C–H oxygenations with H2O2 in the presence of manganese complexes are overviewed. A distinctive feature of catalyst systems of the type Mn complex/H2O2/carboxylic is the existence of two alternative reaction pathways (as found for the oxidation of cumenes), one leading to the formation of alcohol, and the other to ester. The mechanisms of formation of the alcohol and the ester are briefly discussed. Full article
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)
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