Journal of the American Chemical Society
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Chem., Int. Ed. 2014, 53, 7324. (c) Manna, S.; Matcha, K.; Antonchick,
A. P. Angew. Chem., Int. Ed. 2014, 53, 8163.
tions. Calculations were performed on the Extreme Science and
Engineering Discovery Environment (XSEDE), which is support-
ed by the U.S. NSF (OCI-1053575). We are grateful to Professors
Qi-Lin Zhou and Shou-Fei Zhu at Nankai University for kindly
providing some chiral compounds.
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(13) For recent examples, see: (a) Wei, W.-T.; Zhou, M.-B.; Fan, J.-H.;
Liu, W.; Song, R.-J.; Liu, Y.; Hu, M.; Xie, P.; Li, J.-H. Angew. Chem., Int.
Ed. 2013, 52, 3638. (b) Wang, J.; Liu, C.; Yuan, J.; Lei, A. Angew. Chem.,
Int. Ed. 2013, 52, 2256. (c) Moteki, S. A.; Usui, A.; Zhang, T.; Alvarado,
C. R. S.; Maruoka, K. Angew. Chem., Int. Ed. 2013, 52, 8657. (d) O'Brien,
A. G.; Maruyama, A.; Inokuma, Y.; Fujita, M.; Baran, P. S.; Blackmond,
D. G. Angew. Chem., Int. Ed. 2014, 53, 11868.
(14) For recent examples, see: (a) Qin, C.; Jiao, N. J. Am. Chem. Soc.
2010, 132, 15893. (b) Chen, F.; Qin, C.; Cui, Y.; Jiao, N. Angew. Chem.,
Int. Ed. 2011, 50, 11487. (c) Qin, C.; Zhou, W.; Chen, F.; Qu, Y.; Jiao, N.
Angew. Chem., Int. Ed. 2011, 50, 12595. (d) Huang, Z.; Jin, L.; Feng, Y.;
Peng, P.; Yi, H.; Lei, A. Angew. Chem., Int. Ed. 2013, 52, 7151.
(15) For recent examples, see: (a) Yoshimura, A.; Middleton, K. R.; Zhu,
C.; Nemykin, V. N.; Zhdankin, V. V. Angew. Chem., Int. Ed. 2012, 51,
8059. (b) Xu, Z.; Yu, X.; Feng, X.; Bao, M. J. Org. Chem. 2012, 77,
7114.
(16) The treatment of 3a with sodium hydride gave the N-O bond cleav-
age product in 85% yield. For details, see the SI.
(17) We studied the effect of the nitrogen substituents by DFT calcula-
tions. The change of the OMe group to Ph and Me groups increases the C-
H amination barrier from 19.2 kcal/mol (Figure 1a) to 24.7 and 44.3
kcal/mol, respectively. For details, see the SI.
(18) Substrates with secondary and primary C-H bonds and substrates
with aliphatic tethers are unsuccessful. For details, see the SI.
(19) The computed activation free energies for the secondary (2-ethyl-N-
methoxybenzamide) and primary (2-methyl-N-methoxybenzamide) C-H
aminations are 22.4 and 28.5 kcal/mol, much higher than that for the
tertiary one (19.2 kcal/mol, Figure 1a). For details, see the SI.
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(20) As shown below, for substrate 1u, the computed activation free ener-
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lower than that for the secondary C-H amination via transition state TSe.
This is in agreement with the experimentally observed chemoselectivity.
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(21) For the discussion of the radical mechanism, see the SI.
(22) (a) All calculations were performed with: Frisch, M. J., et al. Gaussiꢀ
an 09, Revision D.01; Gaussian Inc.: Wallingford, CT, 2013. (b) Geome-
try optimizations and frequency calculations were performed at the M06-
2X/6-31G(d)[SDD, for I] level. Single-point energy calculations in trifluo-
roethanol (TFE) using the CPCM model were performed at the M06-
2X/6-311+G(d,p)[SDD, for I] level. For details, see the SI.
(23) For recent DFT studies of iodine(III)-mediated reactions, see: (a)
Konnick, M. M.; Hashiguchi, B. G.; Devarajan, D.; Boaz, N. C.; Gunnoe,
T. B.; Groves, J. T.; Gunsalus, N.; Ess, D. H.; Periana, R. A. Angew.
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(24) The formation of oxygen-bonded iodonium cation B' from
intermediate A is calculated to be endergonic by 27.9 kcal/mol in TFE.
(25) Previous study shows that the activation free energy for the
dissociation process is approximately equal to the reaction enthalpy: Wei,
C. S.; Jimenez-Hoyos, C. A.; Videa, M. F.; Hartwig, J. F.; Hall, M. B. J.
Am. Chem. Soc. 2010, 132, 3078. Our calculations indicate that the
dissociation of intermediate B to form nitrenium cation and iodobenzene
is endothermic by 14.2 kcal/mol in terms of enthalpy, and is endergonic
by 1.1 kcal/mol in TFE. Therefore, the activation free energy for the
dissociation of intermediate B is about 14 kcal/mol, higher than that for
the hydride transfer via TSc (about 5 kcal/mol, Figure 1a).
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(28) For the determination of the absolute configuration, see the SI.
(29) Under "DFT-computed conditions" [PhI(OAc)2 as oxidant and TFE
as solvent], the transformation of substrate (S)-1m to product (R)-3m also
occurs with complete stereochemical fidelity. For details, see the SI.
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