Deoxydesulfurization of sulfones derived from dibenzothiophene using nickel compounds

The use of catalytic amounts of compounds of the type [Ni(diphosphine)H] 2 allowed the deoxydesulfurization of dibenzothiophene-sulfones, quantitatively yielding biphenyls. ▪ Catalytic amounts (1 mol%) of [Ni(dippe)H] 2 ( 1), [Ni(dcype)H] 2 ( 2), [Ni(dtbpe)H] 2 ( 3), NiCl 2·6H 2O ( 4) and [Ni(dippe)...

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Published inJournal of molecular catalysis. A, Chemical Vol. 293; no. 1; pp. 65 - 71
Main Authors Oviedo, Alberto, Torres-Nieto, Jorge, Arévalo, Alma, García, Juventino J.
Format Journal Article
LanguageEnglish
Published Amsterdam Elsevier B.V 01.10.2008
Elsevier
Subjects
4,6-Dimethyldibenzothiophene
Biphenyls
Catalysis
Chemistry
Deoxydesulfurization
Deoxygenation
Dibenzothiophene
Exact sciences and technology
General and physical chemistry
Grignard reagents
Nickel
Sulfones
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Deoxygenation
Grignard reagents
4,6-Dimethyldibenzothiophene
Nickel
Deoxydesulfurization
Biphenyls
Sulfones
Dibenzothiophene
Transition element complexes
Hydrocarbon
Sulfone
Organic ligand
Nickel compound
Transition metal
Grignard reagent
Biphenyl
Benzenic compound
Nickel complex
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Summary:The use of catalytic amounts of compounds of the type [Ni(diphosphine)H] 2 allowed the deoxydesulfurization of dibenzothiophene-sulfones, quantitatively yielding biphenyls. ▪ Catalytic amounts (1 mol%) of [Ni(dippe)H] 2 ( 1), [Ni(dcype)H] 2 ( 2), [Ni(dtbpe)H] 2 ( 3), NiCl 2·6H 2O ( 4) and [Ni(dippe)(Me) 2] ( 5) reacted with MeMgBr to yield the straightforward deoxydesulfurization of sulfones of dibenzothiophene (DBTO 2), 4-methyl-dibenzothiophene (MeDBTO 2) and 4,6-dimethyl-dibenzothiophene (Me 2DBTO 2), thereof producing the corresponding sulfur-free biphenyls (85–100% yield) when using a solvent mixture of toluene–THF, 10:2 v/v. The formation of key intermediates of the type [(dippe)Ni(κ 2-( O, O)(sulfone)] play an important role in the activation of the C–S bond in the sulfone as they participate in the ultimate deoxygenation step, even with the more hindered substrates. The formation of MgO and MgS from the catalytic process is envisioned as the driving force for the whole reaction.
ISSN:1381-1169
1873-314X
DOI:10.1016/j.molcata.2008.06.015