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7
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20344373823
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ed. B. Cornils and W. A. Herrmann Wiley-VCH, Weinheim
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R. Taube, in Applied Homogeneous Catalysis with Organometallic Complexes, (ed., (, B. Cornils, and, W. A. Herrmann,) Wiley-VCH, Weinheim, 2002, pp 513-524
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(2002)
Applied Homogeneous Catalysis with Organometallic Complexes
, pp. 513-524
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Taube, R.1
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38
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84961975555
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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
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(2004)
Organometallics
, vol.23
, pp. 4097
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Motta, A.1
Lanza, G.2
Fragala, I.L.3
Marks, T.J.4
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40
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33644931605
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aminoallene substrate: S. Tobisch Chem.-Eur. J. 2006 12 2520
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(2006)
Chem.-Eur. J.
, vol.12
, pp. 2520
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Tobisch, S.1
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43
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78650119602
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Glasgow, 2-7 August
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L. E. N. Allan, D. J. Fox, R. J. Deeth, A. L. Gott and P. Scott, Proceedings of the 42nd IUPAC Congress, Glasgow, 2-7 August 2009
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(2009)
Proceedings of the 42nd IUPAC Congress
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Allan, L.E.N.1
Fox, D.J.2
Deeth, R.J.3
Gott, A.L.4
Scott, P.5
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44
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78650121201
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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.
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48
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78650148038
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‡) can be estimated for the HA of 1 by 2
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‡) can be estimated for the HA of 1 by 2.
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49
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84961975570
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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
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(2008)
Chem.-Eur. J.
, vol.14
, pp. 10430
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Müller, C.1
Koch, R.2
Doye, S.3
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53
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0039785339
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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
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(2000)
J. Am. Chem. Soc.
, vol.122
, pp. 4098
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Senn, H.M.1
Blöchl, P.E.2
Togni, A.3
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58
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77949331957
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For a computational study of organoactinide-assisted intramolecular HA of aminodienes see: S. Tobisch Chem.-Eur. J. 2010 17 3441
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(2010)
Chem.-Eur. J.
, vol.17
, pp. 3441
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Tobisch, S.1
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61
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78650164357
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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.
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62
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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.
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63
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78650131446
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Similar pathways can be imagined for Ln-C bond aminolysis in 4, 5′ via the insertive mechanism
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Similar pathways can be imagined for Ln-C bond aminolysis in 4, 5′ via the insertive mechanism.
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65
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0003412412
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Wiley, New York
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M. B. Smith and J. March, March's Advanced Organic Chemistry, 6th ed., Wiley, New York, 2007, pp. 305-307
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(2007)
March's Advanced Organic Chemistry, 6th Ed.
, pp. 305-307
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Smith, M.B.1
March, J.2
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70
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33748919597
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A. Scholz A. Smola J. Scholz J. Löbel H. Schimann K.-H. Thiele Angew. Chem., Int. Ed. Engl. 1991 30 435
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(1991)
Angew. Chem., Int. Ed. Engl.
, vol.30
, pp. 435
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Scholz, A.1
Smola, A.2
Scholz, J.3
Löbel, J.4
Schimann, H.5
Thiele, K.-H.6
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76
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78650090375
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5 bonds in 4 and 5′ are the dominant pathways towards five-membered and six-membered cyclic amines, respectively
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5 bonds in 4 and 5′ are the dominant pathways towards five-membered and six-membered cyclic amines, respectively
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80
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78650111350
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Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpy barrier
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Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpy barrier.
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81
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-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.
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85
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69349097922
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University of Karlsruhe, Karlsruhe, Germany
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R. Ahlrichs, F. Furche, C. Hättig, W. Klopper, M. Sierka and F. Weigend, TURBOMOLE, version 5.9, University of Karlsruhe, Karlsruhe, Germany, 2006, http://www.turbomole.com
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TURBOMOLE, Version 5.9
-
-
Ahlrichs, R.1
Furche, F.2
Hättig, C.3
Klopper, W.4
Sierka, M.5
Weigend, F.6
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97
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0001104791
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ed. P. v. R. Schleyer, John Wiley, & Sons, Chichester
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A. Klamt, in Encyclopedia of Computational Chemistry, Vol. 1 (Ed.,, P. v. R. Schleyer,), John Wiley, & Sons, Chichester, 1998, pp. 604-615
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Encyclopedia of Computational Chemistry
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Klamt, A.1
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Theoretical Chemistry Institute, University of Wisconsin, Madison, WI
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E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E. Carpenter and F. Weinhold, NBO 4.M, Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 1999
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(1999)
NBO 4.M
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Glendening, E.D.1
Badenhoop, J.K.2
Reed, A.E.3
Carpenter, J.E.4
Weinhold, F.5
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100
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77949327077
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V. G. Malkin, O. L. Malkina, R. Reviakine, A. V. Arbuznikov, M. Kaupp, B. Schimmelpfennig, I. Malkin, M. Repiský, S. Komorovský, P. Hrobarik, E. Malkin, T. Helgaker and K. Ruud, ReSpect program, version 1.2, 2005
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(2005)
ReSpect Program, Version 1.2
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Malkin, V.G.1
Malkina, O.L.2
Reviakine, R.3
Arbuznikov, A.V.4
Kaupp, M.5
Schimmelpfennig, B.6
Malkin, I.7
Repiský, M.8
Komorovský, S.9
Hrobarik, P.10
Malkin, E.11
Helgaker, T.12
Ruud, K.13
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101
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For further details, see http://www.struked.de
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