Selectivity in CH Functionalizations

Shul'pin, G. B.

doi:10.1016/b978-0-08-097774-4.00605-7

Cited by 15 publications

(12 citation statements)

References 239 publications

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“…Methane monooxygenase (MMO) from methane-utilizing bacteria converts alkanes into the corresponding alcohols. Such enzymes oxidize regioselectively n-alkanes to afford predominately (in the case of n-heptane, even exclusively) 2-alcohols [57]. Compound II containing a polynuclear iron complex with chelating oxo-ligands exhibits some features similar to that of binuclear alkane oxygenases, and thus can be considered as an "inorganic alkane oxygenase".…”

Section: Catalytic Oxidation Of Alcohols and Hydrocarbonsmentioning

confidence: 99%

“…The regioselectivity parameter [relative normalized reactivities of H atoms at carbon atoms C(1), C(2), C(3), and C(4) of n-octane chain] determined for the oxidation of n-octane is relatively low, i.e., C(1):C(2):C(3):C(4) = 1.0:6.7:6.6:6.1. It can be seen that hydrogen atoms in position 4 posess lower activity, aparently due to some sterical hindrance [50,57,60]. The bond-selectivity parameter (1 • :2 • :3 • ; the relative normalized reactivities of hydrogen atoms at the primary, secondary, and tertiary carbons) in the oxidation of methylcyclohexane (1.0:6.7:17.5) is close to the corresponding values found for the systems oxidizing alkanes with hydroxyl radicals (see, for example, References [69][70][71][72][73][74][75]).…”

Section: Selectivity In the Alkane Oxidationsmentioning

confidence: 99%

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High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

et al. 2017

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Section: Catalytic Oxidation Of Alcohols and Hydrocarbonsmentioning

confidence: 99%

Section: Selectivity In the Alkane Oxidationsmentioning

confidence: 99%

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

et al. 2017

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“…Such enzymes oxidize regioselectively n-alkanes to afford predominately (in the case of n-heptane even exclusively) 2-alcohols [57]. Compound II containing a polynuclear iron complex with chelating oxo-ligands exhibits some features similar to that of binuclear alkane oxygenases, and thus can be considered as an "inorganic alkane oxygenase".…”

Section: Catalytic Oxidation Of Alcohols and Hydrocarbonsmentioning

confidence: 99%

“…C(1) : C(2) : C(3) : C(4) = 1.0 : 6.7 : 6.6 : 6.1. It can be seen that hydrogen atoms in position 4 posess lower activity, aparently due to some sterical hindrance [50,57,60]. The bond-selectivity parameter (1° : 2° : 3°; the relative normalized reactivities of hydrogen atoms at the primary, secondary and tertiary carbons) in the oxidation of methylcyclohexane (1.0 : 6.7 : 17.5) is close to the corresponding values found for the systems oxidizing alkanes with hydroxyl radicals (see, for example, Refs.…”

Section: Selectivity In the Alkane Oxidationsmentioning

confidence: 99%

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

Yalymov

Bilyachenko

Levitsky

et al. 2017

Preprint

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Two types of heterometallic (Fe(III),Na) silsesquioxanes [Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(MeCN)4.5.1.25(MeCN), I, and [Ph5Si5O10]2[Ph4Si4O8]2Fe6Na6(O2‒)3(MeCN)8.5(H2O)8.44, II, were obtained and characterized. X-Ray studies established distinctive structures of both products, with pair of Fe(III)-O-based triangles surrounded by siloxanolate ligands, giving fascinating cage architectures. Complex II proved to be catalytically active in the formation of amides from alcohols and amines, thus becoming a rare example of metallasilsesquioxanes performing homogeneous catalysis. Benzene, cyclohexane and other alkanes, as well as alcohols, can be oxidized in acetonitrile solution to phenol, the corresponding alkyl hydroperoxides and ketones, respectively, by hydrogen peroxide in air in the presence of catalytic amounts of complex II and trifluoroacetic acid. Thus, the cyclohexane oxidation at 20 °C gave oxygenates in very high for alkanes yield (48% based on alkane). The kinetic behaviour of the system indicates that the mechanism includes the formation of hydroxyl radicals generated from hydrogen peroxide in its interaction with diiron species. The latter are formed via monomerization of starting hexairon complex with further dimerization of the monomers.

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“…Organic and inorganic peroxides and especially hydrogen peroxide are widely employed for the oxidation of various organic compounds. Alkanes are also among these organic substrates, although saturated hydrocarbons exhibit very high inertness in reactions in solutions under mild conditions [1][2][3][4][5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

et al. 2019

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Reactions of [VCl3(thf)3] or VBr3 with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) in a 1:1 molar ratio in air under solventothermal conditions has afforded polymeric oxidovanadium(IV) four complexes 1–4 of a general formula [VO(L)X2]n (L = bpy, phen and X = Cl, Br). Monomeric complex [VO(DMF)(phen)Br2] (4a) has been obtained by the treatment of compound 4 with DMF. The complexes were characterized by IR spectroscopy and elemental analysis. The crystal structures of 3 and 4a were determined by an X-ray diffraction (XRD) analysis. The {VOBr2(bpy)} fragments in 3 form infinite chains due to the V = O…V interactions. The vanadium atom has a distorted octahedral coordination environment. Complexes 1–4 have been tested as catalysts in the homogeneous oxidation of alkanes (to produce corresponding alkyl hydroperoxides which can be easily reduced to alcohols by PPh3) and alcohols (to corresponding ketones) with H2O2 or tert-butyl hydroperoxide in MeCN. Compound 1 exhibited the highest activity. The mechanism of alkane oxidation was established using experimental selectivity and kinetic data and theoretical DFT calculations. The mechanism is of the Fenton type involving the generation of HO• radicals.

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Selectivity in CH Functionalizations

Cited by 15 publications

References 239 publications

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

High Catalytic Activity of Heterometallic (Fe<sub>6</sub>Na<sub>7 </sub>and Fe<sub>6</sub>Na<sub>6</sub>) Cage Silsesquioxanes in Oxidations with Peroxides

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

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