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Volumn 40, Issue 1, 2011, Pages 249-261

Mechanistic investigation of organolanthanide-mediated hydroamination of aminoallenes: A comprehensive computational assessment of various routes for allene activation

Author keywords

[No Author keywords available]

Indexed keywords

AMINO PROTON; AMINOLYSIS; C-C BONDS; CYCLISATIONS; DOUBLE BONDS; EMPIRICAL RATE LAW; HYDROAMINATIONS; INTRAMOLECULAR HYDROAMINATION; KEY FEATURE; LANTHANIDES; MECHANISTIC STUDIES; ORGANOLANTHANIDES; RATE LAWS; RESTING STATE; RING CLOSURES; STARTING MATERIALS;

EID: 78650120872     PISSN: 14779226     EISSN: 14779234     Source Type: Journal    
DOI: 10.1039/c0dt00819b     Document Type: Conference Paper
Times cited : (13)

References (101)
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    • For computational studies of organolanthanide-assisted intramolecular HA of various substrate classes, see: aminoalkene substrates: A. Motta G. Lanza I. L. Fragala T. J. Marks Organometallics 2004 23 4097
    • (2004) Organometallics , vol.23 , pp. 4097
    • Motta, A.1    Lanza, G.2    Fragala, I.L.3    Marks, T.J.4
  • 40
  • 44
    • 78650121201 scopus 로고    scopus 로고
    • Note that the rate-limiting step of the insertive mechanism is not identical for the various substrate classes; cyclisation is the rate-limiting event for aminoalkenes/-alkynes (reference 3a,b), whilst for aminoallenes/-dienes protonolysis is turnover limiting (reference 3c,d) A possible explanation for the observed KIE in aminoalkene HA in the context of the Ln-N σ-bond insertive mechanism with turnover-limiting cyclisation is given in reference 2b
    • Note that the rate-limiting step of the insertive mechanism is not identical for the various substrate classes; cyclisation is the rate-limiting event for aminoalkenes/-alkynes (reference 3a,b), whilst for aminoallenes/-dienes protonolysis is turnover limiting (reference 3c,d) A possible explanation for the observed KIE in aminoalkene HA in the context of the Ln-N σ-bond insertive mechanism with turnover-limiting cyclisation is given in reference 2b.
  • 48
    • 78650148038 scopus 로고    scopus 로고
    • ‡) can be estimated for the HA of 1 by 2
    • ‡) can be estimated for the HA of 1 by 2.
  • 49
    • 84961975570 scopus 로고    scopus 로고
    • For computational studies of group 4 transition metal-assisted intramolecular HA of various substrate classes, see: aminoalkene substrates: C. Müller R. Koch S. Doye Chem.-Eur. J. 2008 14 10430
    • (2008) Chem.-Eur. J. , vol.14 , pp. 10430
    • Müller, C.1    Koch, R.2    Doye, S.3
  • 53
    • 0039785339 scopus 로고    scopus 로고
    • For computational studies of transition metal- and organolanthanideassisted intermolecular HA, see H. M. Senn P. E. Blöchl A. Togni J. Am. Chem. Soc. 2000 122 4098
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 4098
    • Senn, H.M.1    Blöchl, P.E.2    Togni, A.3
  • 58
    • 77949331957 scopus 로고    scopus 로고
    • For a computational study of organoactinide-assisted intramolecular HA of aminodienes see: S. Tobisch Chem.-Eur. J. 2010 17 3441
    • (2010) Chem.-Eur. J. , vol.17 , pp. 3441
    • Tobisch, S.1
  • 61
    • 78650164357 scopus 로고    scopus 로고
    • 2Lu-amido catalyst (reference 3c), which used a different (BP86) DFT method. The present study can be regarded as being superior, because of the applied state-of-the-art methodology that involves a more consistent treatment of the authentic reaction conditions, together with the usage of the modern, almost nonempirical, well-performing meta-GGA TPSS functional, as detailed in the computational methodology section
    • 2Lu-amido catalyst (reference 3c), which used a different (BP86) DFT method. The present study can be regarded as being superior, because of the applied state-of-the-art methodology that involves a more consistent treatment of the authentic reaction conditions, together with the usage of the modern, almost nonempirical, well-performing meta-GGA TPSS functional, as detailed in the computational methodology section.
  • 62
    • 78650117622 scopus 로고    scopus 로고
    • Substrate association and dissociation steps are known to be facile in organolanthanide-mediated intramolecular HA. For NMR evidence of rapid association/dissociation of free amine and of amido/amine permutation see reference 2b
    • Substrate association and dissociation steps are known to be facile in organolanthanide-mediated intramolecular HA. For NMR evidence of rapid association/dissociation of free amine and of amido/amine permutation see reference 2b.
  • 63
    • 78650131446 scopus 로고    scopus 로고
    • Similar pathways can be imagined for Ln-C bond aminolysis in 4, 5′ via the insertive mechanism
    • Similar pathways can be imagined for Ln-C bond aminolysis in 4, 5′ via the insertive mechanism.
  • 76
    • 78650090375 scopus 로고    scopus 로고
    • 5 bonds in 4 and 5′ are the dominant pathways towards five-membered and six-membered cyclic amines, respectively
    • 5 bonds in 4 and 5′ are the dominant pathways towards five-membered and six-membered cyclic amines, respectively
  • 80
    • 78650111350 scopus 로고    scopus 로고
    • Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpy barrier
    • Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpy barrier.
  • 81
    • 78650149864 scopus 로고    scopus 로고
    • -1 (Fig. 10) for the most accessible pathways of the selectivity-determining and turnover-limiting aminolysis that leads to P6s/P6a corresponds to a P6s:P6a ratio of 66:34 (298.15 K) upon application of Stefan-Boltzmann statistics. A more detailed analysis can be found in reference 3c
    • -1 (Fig. 10) for the most accessible pathways of the selectivity-determining and turnover-limiting aminolysis that leads to P6s/P6a corresponds to a P6s:P6a ratio of 66:34 (298.15 K) upon application of Stefan-Boltzmann statistics. A more detailed analysis can be found in reference 3c.
  • 97
    • 0001104791 scopus 로고    scopus 로고
    • ed. P. v. R. Schleyer, John Wiley, & Sons, Chichester
    • A. Klamt, in Encyclopedia of Computational Chemistry, Vol. 1 (Ed.,, P. v. R. Schleyer,), John Wiley, & Sons, Chichester, 1998, pp. 604-615
    • (1998) Encyclopedia of Computational Chemistry , vol.1 , pp. 604-615
    • Klamt, A.1
  • 101
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    • For further details, see http://www.struked.de


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