Ruthenium-mediated amidation of saturated C–H bonds and crystal structure of a bis(tosyl)amidoruthenium(III) complex of 1,4,7-trimethyl-1,4,7-triazacyclononane

Au, Sze Man; Zhang, Suo Bo; Fung, Wai Hong; Yu, Wing Yiu; Ming, Chi; Cheung, Ka Shing

doi:10.1039/a808048h

Cited by 45 publications

(13 citation statements)

References 13 publications

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“…[25] After these works, various kinds of catalytic systemsw ere appliedt oC ÀHa mination by severalg roups,i ncluding those of Che, PØrez, Cenini, and He. [26] Following seminalr eports by Müller, [23b] asymmetric CÀHa minations by using PhI=NTsw ere mainly developed by the Che [26c, 27a] and Katsukig roups. [27b] Further studies of CÀHa mination catalyzed by dirhodium(II,II) complexes were developed by Müller,D auban, and Dodd.…”

Section: Iminoiodinanesmentioning

confidence: 99%

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Shimbayashi

Sasakura

Eguchi

et al. 2018

Chemistry A European J

120

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Nitrene-transfer reactions have been a powerful synthetic method for direct incorporation of nitrogen atoms into organic molecules. Discovery of novel nitrene-transfer reactions has been dominantly supported by not only the improvement in transition-metal catalysts but also by the employment of novel precursors of nitrenoids. Since the pioneering works utilizing organic azides or iminoiodinanes as practical synthetic tools for nitrogen-containing compounds were reported, a new approach using various N-heterocycles containing strain energy or a weak bond has emerged. In this review, we briefly summarize the history of nitrene-transfer chemistry from the viewpoint of its precursors. In particular, the use of N-heterocycles such as 2H-azirines, 1,4,2-dioxazol-5-ones, 1,2,4-oxadiazol-5-ones, isoxazol-5(4H)-ones, and isoxazoles are comprehensively described, showing the recent remarkable progress in this chemistry.

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Section: Iminoiodinanesmentioning

confidence: 99%

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Shimbayashi

Sasakura

Eguchi

et al. 2018

Chemistry A European J

120

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“…The present work deals with the PhINTs amidation of hydrocarbons catalyzed by ruthenium non-porphyrin complexes 2 and 3 , which proceeds probably via sulfonylimido insertion into saturated C−H bonds. Moreover, like electron-deficient manganese porphyrin [Mn(TPFPP)Cl], complexes 2b and 3 can catalyze the amidation directly with commercially available PhI(OAc) 2 /TsNH 2 without the necessity to pre-isolate PhINTs .…”

Section: Introductionmentioning

confidence: 99%

Amidation of Unfunctionalized Hydrocarbons Catalyzed by Ruthenium Cyclic Amine or Bipyridine Complexes

et al. 2000

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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.

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“…The development of metal-mediated nitrogen atom transfer reactions such as aziridination of alkenes, − amination of alkanes, and allylic amination of alkenes − has received considerable attention in recent years. The best explored systems to date are those employing ( N -( p -tolylsulfonyl)imino)phenyliodinane (PhINTs) as the nitrogen source.…”

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confidence: 99%

Aziridination of Alkenes and Amidation of Alkanes by Bis(tosylimido)ruthenium(VI) Porphyrins. A Mechanistic Study

et al. 1999

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Bis(tosylimido)ruthenium(VI) porphyrins, [RuVI(Por)(NTs)2] (Por = TPP, TTP, 4-Cl-TPP, 4-MeO-TPP, OEP), were prepared in 60−74% yields by treatment of [RuII(Por)(CO)(MeOH)] with (N-(p-tolylsulfonyl)imino)phenyliodinane (PhINTs) in dichloromethane. In dichloromethane containing pyrazole, they reacted with alkenes or alkanes to give tosylamidoruthenium(IV) porphyrins, [RuIV(Por)(NHTs)(pz)], in about 75% yields. The reactions of [RuVI(TPP)(NTs)2] and [RuVI(OEP)(NTs)2] with styrene, para-substituted styrenes, norbornene, cyclooctene, and β-methylstyrene afforded the corresponding N-tosylaziridines in 66−85% yields. The aziridination of cis-stilbene and cis-β-methylstyrene by [RuVI(Por)(NTs)2] is nonstereospecific with a partial loss of the alkene stereochemistry. Kinetic studies on the reactions between [RuVI(TPP)(NTs)2] and 16 alkenes (cyclooctene, norbornene, 2,3-dimethyl-2-butene, styrene, para-substituted styrenes, α- and β-methylstyrene, and α- and β-deuteriostyrene) gave the second-order rate constants (k 2) ranging from (1.60 ± 0.06) × 10 - 3 to (90 ± 4) × 10 - 3 dm3 mol - 1 s - 1 at 298 K. The slope of the linear plot of log k 2 vs E 1/2 for eight representative alkenes was found to be −1.7 V - 1. In the case of para-substituted styrenes, linear correlation between log k R (k R = relative rate) and σ+ gives a ρ+ value as small as −1.1. However, the effect of para substituents on k R can be best accounted for by considering both the polar and spin delocalization effect. Measurements on the secondary deuterium isotope effect revealed that only the β-carbon atom of styrene experienced a significant change in its hybridization in reaching the transition state. All these are consistent with rate-determining formation of a carboradical intermediate. The reactions of [RuVI(TPP)(NTs)2] and [RuVI(OEP)(NTs)2] with adamantane, cyclohexene, ethylbenzene, and cumene resulted in tosylamidation of these hydrocarbons and afforded the corresponding amides in 52−88% yields. For cyclohexane and toluene, the tosylamidation products were formed in poor yields (ca. 10%). Kinetic studies on the reactions between [RuVI(TPP)(NTs)2] and nine hydrocarbons (cumene, ethylbenzene, cyclohexene, and para-substituted ethylbenzenes) gave the second-order rate constants (k 2) in the range of (0.330 ± 0.008) × 10-3 to (16.5 ± 0.3) × 10-3 dm3 mol-1 s-1. These reactions exhibit a large primary deuterium isotope effect, with a k H/k D ratio of 11 for the tosylamidation of ethylbenzene. In the case of para-substituted ethylbenzenes, both electron-donating and -withdrawing substituents moderately promote the reaction. There is an excellent linear correlation between log k R and a related carboradical parameter. On the basis of these observations, a mechanism involving the rate-limiting formation of a carboradical intermediate is postulated.

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Ruthenium-mediated amidation of saturated C–H bonds and crystal structure of a bis(tosyl)amidoruthenium(III) complex of 1,4,7-trimethyl-1,4,7-triazacyclononane

Cited by 45 publications

References 13 publications

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Recent Progress on Cyclic Nitrenoid Precursors in Transition‐Metal‐Catalyzed Nitrene‐Transfer Reactions

Amidation of Unfunctionalized Hydrocarbons Catalyzed by Ruthenium Cyclic Amine or Bipyridine Complexes

Aziridination of Alkenes and Amidation of Alkanes by Bis(tosylimido)ruthenium(VI) Porphyrins. A Mechanistic Study

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