Selective amidation of simple hydrocarbons with pre-isolated and in-situ formed iminoiodanes catalyzed by ruthenium complexes [Ru(III)(Me(3)tacn)(CF(3)CO(2))(3).H(2)O] (2b, Me(3)tacn = N,N', N"-trimethyl-1,4,7-triazacyclononane) and cis-[Ru(II)(6, 6'-Cl(2)bpy)(2)Cl(2)] (3, 6,6'-Cl(2)bpy = 6,6'-dichloro-2, 2'-bipyridine) was investigated. With PhI=NTs as nitrogen source, both catalysts efficiently promote the amidation of adamantane, cyclohexene, ethylbenzene, cumene, indan, tetralin, and diphenylmethane to afford N-substituted sulfonamides in 80-93% yields with high selectivity. Competitive amidations of para-substituted ethylbenzenes and kinetic isotope effect for the amidation of cyclohexene/cyclohexene-d(10) suggest that the amidation processes probably proceed via the hydrogen abstraction by a reactive Ru=NTs species to form a carboradical intermediate. The amidation with PhI(OAc)(2)/TsNH(2) gave results comparable to those obtained with PhI=NTs. Extension of the "PhI(OAc)(2)/TsNH(2) + catalyst 2b or 3" protocol to MeSO(2)NH(2) and PhCONH(2) with ethylbenzene as substrate produced the corresponding N-substituted amides in up to 89% yield.

Bis(tosyl)imidoruthenium(VI) porphyrin complexes are prepared and characterised by spectroscopic means; [Ru VI -(tpp)(NTs) 2 ] can undergo imido group transfer reactions with alkenes to afford aziridines, as well as C-H bond oxidation of benzyl alcohol to give benzaldehyde; a tosylamido ruthenium(IV) complex is also isolated and characterised by X-ray diffraction.

The bis(tosylimido)osmium(VI) porphyrins [Os(VI)(Por)(NTs)(2)] [Por = tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), meso-tetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(4-methoxyphenyl)porphyrinato (4-MeO-TPP); Ts = tosyl] were prepared from the reactions of [Os(II)(Por)(CO)(MeOH)] with excess PhI=NTs in dichloromethane. The X-ray crystal structure of [Os(VI)(TPP)(NTs)(2)] has been determined. Crystal data for [Os(VI)(TPP)(NTs)(2)]: triclinic, space group P&onemacr; (No. 2), a = 10.836(3) Å, b = 12.067(4) Å, c = 19.647(6) Å, alpha = 94.05(3) degrees, beta = 93.88(3) degrees, gamma = 104.65(3) degrees, V = 2469(1) Å(3), Z = 2, R (R(w)) = 0.030 (0.038), goodness-of-fit = 1.19. The mean Os=NTs distance is 1.800 Å. The Os-N-S angles average 155.8 degrees. Reaction of [Os(VI)(TPP)(NTs)(2)] with triphenylphosphine gives Ph(3)P=NTs and [Os(II)(TPP)(PPh(3))(2)].

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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.