Catalytic addition of secondary amines to ethylene (Contribution No. 1720)

Coulson, D. R.

doi:10.1016/s0040-4039(01)96459-7

Cited by 101 publications

(60 citation statements)

References 2 publications

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“…The hydroamination of norbornene with aniline was selected [Equation (6)], (see Table 2). As expected, [47,48] no reaction was observed when thf was used as solvent (run 1, Table 2). The use of different imidazolium chlorides resulted in only traces of reaction products (runs 2 and 3).…”

Section: Hydroamination Of Norbornene By Aniline In Ionic Liquidssupporting

confidence: 84%

Platinum‐Catalyzed Intermolecular Hydroamination of Alkenes: Halide‐Anion‐Promoted Catalysis

2007

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Tetraalkylphosphonium halides play the role of “promoters” for the previously unknown PtII‐catalyzed hydroamination of alkenes. The promoting effect of these “cocatalysts” depends only upon their anionic moiety. The PtII/nBu4PBr system exhibits an unprecedented catalytic activity (aerobic conditions) for the hydroamination of ethylene and 1‐hexene (regioselectivity > 95 %, Markovnikov).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Hydroamination Of Norbornene By Aniline In Ionic Liquidssupporting

confidence: 84%

Platinum‐Catalyzed Intermolecular Hydroamination of Alkenes: Halide‐Anion‐Promoted Catalysis

2007

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“…Intermolecular hydroaminations [1,3] are developed to a much lesser extent and the hydroamination of the simplest olefin (ethylene) has been a research focus of continuing interest. The catalytic hydroamination of ethylene with secondary amines in the presence of rhodium and iridium compounds was reported in 1971, [4] and in subsequent years a variety of catalysts based on these two metals were identified. [5] The stochiometric addition of secondary amines to coordinated ethylene in platinum compounds was reported between 1968 and 1973, [6] and catalytic variants recently employed platinum salts, such as platinum bromide.…”

Section: Introductionmentioning

confidence: 99%

A Computational Study of Rhodium Pincer Complexes with Classical and Nonclassical Hydride Centres as Catalysts for the Hydroamination of Ethylene with Ammonia

Uhe¹,

Hölscher²,

Leitner³

2010

Chemistry A European J

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The catalytic hydroamination of ethylene with ammonia was investigated by means of density functional theory (DFT) calculations. An initial computational screening of key reaction steps (C-N bond formation, N-H bond cleavage), which are assumed to be part of a catalytic cycle, was carried out for complexes with the [M(L)]-complex fragment (M=Rh, Ir; L=NCN, PCP; NCN=2,5-bis(dimethylaminomethyl)benzene, PCP=2,5-bis- (dimethylphosphanylmethyl)benzene). Based on the evaluation of activation barriers, this screening showed the rhodium compound with the NCN ligand to be the most promising catalyst system. A detailed investigation was carried out starting with the hypothetical catalyst precursor [Rh(NCN)(H)(2)(H(2))] (1). A variety of activation pathways to yield the catalytically active species [Rh(NCN)(H)(NH(2))] (5), as well as [Rh(NCN)(C(2)H(5))(NH(2))] (17), were identified. With 5 and 17 several closed catalytic cycles could be calculated. One of the calculated cycles is favoured kinetically and bond-forming events have activation barriers low enough to be put into practice. The calculations also show that for experimental realisation the synthesis of 1 is not necessary, as the synthesis of 17 would establish an active catalyst directly without the need for activation. Oligomerisation of ethylene would be possible in principle and would be expected as a competitive side reaction. Accordingly not only ethylamine would be observed in an experimental system, as amines with longer carbon chains also can be formed.

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“…In general, the advantage of late-transition-metal catalysts is their greater tolerance of polar functional groups. The first successful demonstration of this process was with Rh III [24] and Ir III [25] complexes. More recently, Ru 3 (CO) 12 [26,27] and [Rh- [28] (cod = cyclooctadiene) have been applied to the catalytic intermolecular hydroamination of aniline derivatives and terminal alkynes.…”

Section: Resultsmentioning

confidence: 99%

Development, Scope and Mechanisms of Multicomponent Reactions of Asymmetric Electron‐Deficient Alkynes with Amines and Formaldehyde

Cao

Wang

Jiang

et al. 2008

Chemistry A European J

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Based on the reactive behaviour of the substrates, two synthetic routes to polysubstituted pyrimidine derivatives are presented herein: 1) A catalyst-free multicomponent reaction of electron-deficient alkynes, aliphatic amines and formaldehyde and 2) Ag(I)-catalyzed synthesis of pyrimidines from electron-deficient alkynes, anilines and formaldehyde by a domino reaction. Under optimized conditions, the multicomponent reactions were accomplished with high regioselectivity and excellent yields. A computational study was carried out by using the B3LYP density functional theory to elucidate the mechanisms of the catalyst-free hydroamination reaction. Calculations showed the activation free energies of aliphatic amines were lower than those of anilines, which is consistent with the experimental results.

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Catalytic addition of secondary amines to ethylene (Contribution No. 1720)

Cited by 101 publications

References 2 publications

Platinum‐Catalyzed Intermolecular Hydroamination of Alkenes: Halide‐Anion‐Promoted Catalysis

Platinum‐Catalyzed Intermolecular Hydroamination of Alkenes: Halide‐Anion‐Promoted Catalysis

A Computational Study of Rhodium Pincer Complexes with Classical and Nonclassical Hydride Centres as Catalysts for the Hydroamination of Ethylene with Ammonia

Development, Scope and Mechanisms of Multicomponent Reactions of Asymmetric Electron‐Deficient Alkynes with Amines and Formaldehyde

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