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33847001063
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Although the GM reaction is reversible, we have depicted the isomerization of 1a to 5a in a single direction for clarity
-
Although the GM reaction is reversible, we have depicted the isomerization of 1a to 5a in a single direction for clarity.
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33846943147
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We note that the radical derived from initial H atom abstraction from C3 of 1a lies 24.8 kJ mol-1 higher in energy than 2a
-
-1 higher in energy than 2a.
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54
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33846942435
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We note that if hydrogen abstraction were to occur from C3 of 1b, then the resulting radical would be 24.4 kJ mol-1 higher in energy than 2b
-
-1 higher in energy than 2b.
-
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61
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0033551437
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See, for example: a
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64
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33846976855
-
-
It should be kept in mind that the RSEs measure the effect of a substituent in the radical relative to its effect in the corresponding closed-shell molecule which may not be negligible, but for simplicity we do not always repeat this cautionary comment
-
It should be kept in mind that the RSEs measure the effect of a substituent in the radical relative to its effect in the corresponding closed-shell molecule (which may not be negligible), but for simplicity we do not always repeat this cautionary comment.
-
-
-
-
65
-
-
33846957534
-
-
Because of numerical rounding, differences in the BDEs of Table 1 may not reproduce the tabulated RSEs to the accuracy quoted.
-
Because of numerical rounding, differences in the BDEs of Table 1 may not reproduce the tabulated RSEs to the accuracy quoted.
-
-
-
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66
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See, for example: a
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See, for example: (a) Armstrong, D. A.; Yu, D.; Rauk, A. Can. J. Chem. 1996, 74, 1192-7207.
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33846959972
-
-
See the Supporting Information for an expanded discussion of the use of RSEs to assess the propensity of isomerization to occur within the GM-catalyzed reactions using a specific example of the hypothetical isomerization of 2,2-diaminoglutaric acid
-
See the Supporting Information for an expanded discussion of the use of RSEs to assess the propensity of isomerization to occur within the GM-catalyzed reactions using a specific example of the hypothetical isomerization of 2,2-diaminoglutaric acid.
-
-
-
-
71
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33749022253
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Yoon, M.; Patwardhan, A.; Qiao, C.; Mansoorabadi, S. O.; Menefee, A. L.; Reed, G. H.; Marsh, E. N. G. Biochemistry 2006, 45, 11650-11657.
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72
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33846980960
-
-
We note that if hydrogen abstraction were to occur from C3 of 1c, then the resulting radical would be 19.1 kJ mol-1 higher in energy than 2c
-
-1 higher in energy than 2c.
-
-
-
-
73
-
-
33846990694
-
-
We note that if hydrogen abstraction were to occur from C3 of 1d, then the resulting radical would be 20.8 kJ mol-1 higher in energy than 2d
-
-1 higher in energy than 2d.
-
-
-
-
74
-
-
33846996149
-
-
-1 between 3d* and 2d, we estimate that less than 0.2% of 2d would be present at 298 K.
-
-1 between 3d* and 2d, we estimate that less than 0.2% of 2d would be present at 298 K.
-
-
-
-
75
-
-
33846974176
-
-
See section 3.5.2
-
See section 3.5.2.
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Smith, D. M.; Golding, B. T.; Radom, L. J. Am. Chem. Soc. 1999, 121, 1037-1044.
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(1999)
J. Am. Chem. Soc
, vol.121
, pp. 1037-1044
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Smith, D.M.1
Golding, B.T.2
Radom, L.3
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80
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33846958922
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We find the C3-derived substrate radical of 1f to lie 21.5 kJ mol-1 higher in energy than 2f
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-1 higher in energy than 2f.
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81
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33846960558
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-1 for the isomerization of 2-ketoglutaric acid to 3-methyloxaloacetic acid depicted in Scheme 6, we estimate that less than 2.1% of the product would be present at 298 K.
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-1 for the isomerization of 2-ketoglutaric acid to 3-methyloxaloacetic acid depicted in Scheme 6, we estimate that less than 2.1% of the product would be present at 298 K.
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