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We note that the transition structures obtained for the hydrogen-abstraction steps are not necessarily those of lowest energy. The latter lead in some cases to unrealistically small hydrogen-abstraction barriers as a result of strong intermolecular hydrogen bonding between the substrate and the model for Ado-H. We aimed to avoid or minimize the impact of such artificially introduced intermolecular interactions in a consistent manner. For the initial hydrogen-abstraction reaction, Ado· was always positioned orthogonal to the plane of the C-C bond at Cl of the substrate and then optimized, while for the hydrogen re-abstraction reaction, Ado-H was always positioned collinear to the plane of the C-C bond at C2 of the substrate and then optimized.
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It should be noted that, while the relative energies of 3b and 4b from the ONIOM QM/MM calculations of ref 7 for the protonated His143 model are in qualitative agreement with the EPR data of ref 36, this does not say anything about the rearrangement mechanism to convert 3b to 4b. Indeed, with the protonated His 143 model the rearrangement step led to dissociation of 3b to form an aldehyde radical plus water. On the basis of this result, the authors of ref 7 have argued against the dominant involvement of protonated His 143 in the facilitation of the 1,2-OH shift.
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Note that Scheme 2b represents a quantification of Scheme 1b; see Introduction.
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(b) Smith, D. M.; Golding, B. T.; Radom, L. J. Am. Chem. Soc. 1999, 121, 1383-1384.
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Smith, D.M.1
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0034684268
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(c) Wetmore, S. D.; Smith, D. M.; Radom, L. J. Am. Chem. Soc. 2000, 122, 10208-10209.
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0034834182
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(d) Wetmore, S. D.; Smith, D. M.; Golding, B. T.; Radom, L. J. Am. Chem. Soc. 2001, 123, 7963-7972.
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Wetmore, S.D.1
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86
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0035850525
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(e) Wetmore, S. D.; Smith, D. M.; Radom, L. J. Am. Chem. Soc. 2001, 123, 8678-8689.
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Wetmore, S.D.1
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88
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0037184475
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(g) Wetmore, S. D.; Smith, D. M.; Bennett, J. T.; Radom, L. J. Am. Chem. Soc. 2002, 124, 14054-14065.
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Wetmore, S.D.1
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Bennett, J.T.3
Radom, L.4
-
90
-
-
33644933491
-
-
note
-
The terms "push" and "pull" relate to the location of the catalytic moiety with respect to the migrating group. If the catalytic moiety is located adjacent to the origin of the migration it is deemed to be "pushing", whereas if it is located adjacent to the endpoint of the migration it is deemed to be "pulling".
-
-
-
-
92
-
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0037590083
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-
Shibata, N.; Nakanishi, Y.; Fukuoka, M.; Yamanishi, M.; Yasuoka, N.; Toraya, T. J. Biol. Chem. 2003, 278, 22717-22725.
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, pp. 22717-22725
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Shibata, N.1
Nakanishi, Y.2
Fukuoka, M.3
Yamanishi, M.4
Yasuoka, N.5
Toraya, T.6
-
93
-
-
33644944359
-
-
note
-
Potassium ion coordination is in a bridging arrangement analogous to that found in the crystal structure.
-
-
-
-
94
-
-
33644937121
-
-
note
-
Although FH has no direct counterpart in biological systems, it is used here to model the effect of a weak neutral (gas-phase) acid.
-
-
-
-
96
-
-
0035901673
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-
See, for example: Fischer, H.; Radom, L. Angew. Chem., Int. Ed. 2001, 40, 1340-1371.
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(2001)
Angew. Chem., Int. Ed.
, vol.40
, pp. 1340-1371
-
-
Fischer, H.1
Radom, L.2
-
97
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-
0035980224
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-
For a revised value of the tritium isotope effect for DDH for the transfer of tritium from 5′-deoxyadenosine to product, see: Chih, H.-W.; Marsh, E. N. G. Biochemistry 2001, 40, 13060-13067.
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(2001)
Biochemistry
, vol.40
, pp. 13060-13067
-
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Chih, H.-W.1
Marsh, E.N.G.2
-
99
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0033577302
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-
See, for example: Alhambra, C.; Gao, J.; Corchado, J. C.; Villà, J.; Truhlar, D. G. J. Am. Chem. Soc. 1999, 121, 2253-2258.
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(1999)
J. Am. Chem. Soc.
, vol.121
, pp. 2253-2258
-
-
Alhambra, C.1
Gao, J.2
Corchado, J.C.3
Villà, J.4
Truhlar, D.G.5
-
100
-
-
33644940721
-
-
note
-
tun values to the number of digits quoted.
-
-
-
-
101
-
-
33845377664
-
-
Viehe, H.-G.; Janousek, Z.; Merényi, R.; Stella, L. Acc. Chem. Res. 1985, 18, 148-154.
-
(1985)
Acc. Chem. Res.
, vol.18
, pp. 148-154
-
-
Viehe, H.-G.1
Janousek, Z.2
Merényi, R.3
Stella, L.4
-
102
-
-
33644945924
-
-
note
-
-1.
-
-
-
-
103
-
-
33644946836
-
-
note
-
-1 imaginary frequency for the symmetrical species, one may therefore consider that under thermal equilibrium conditions the cyano complex is effectively symmetrical.
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