Organic Letters
Letter
Chem. Theory Comput. 2010, 6, 1990. M06-2X: (g) Zhao, Y.; Truhlar,
D. G. Theor. Chem. Acc. 2008, 120, 215. (h) Zhao, Y.; Truhlar, D. G.
Acc. Chem. Res. 2008, 41, 157.
AUTHOR INFORMATION
Corresponding Authors
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Notes
(8) See Figure S1 in Supporting Information for the computed
structures.
(9) A methyl shift is much higher in energy and was not observed by
computation.
The authors declare no competing financial interest.
(10) (a) Brand, J. P.; Charpentier, J.; Waser, J. Angew. Chem., Int. Ed.
2009, 48, 9346. (b) Fernandez Gonzalez, D.; Brand, J. P.; Waser, J.
Chem. - Eur. J. 2010, 16, 9457.
ACKNOWLEDGMENTS
We thank the European Research Council, Starting Grant
iTools4MC, Number 334840, for financial support. M.D.W.
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(11) Preliminary computations were also performed with phenolate
and tolyl anions as nucleophiles. For the case of the oxygen
nucleophile, pathways corresponding to α and β addition could also
be identified and were close in energy. For the carbon nucleophile, the
β addition pathway via preliminary interaction with the iodine atom
could not be easily located and requires further study.
(12) The fact that the transition state energy of the α pathway is
lower for methoxy than methyl could be tentatively explained by the
inductive effect of the oxygen atom.
́
thanks Prof. Clemence Corminboeuf (EPFL) for helpful
suggestions and comments. The Laboratory for Computational
Molecular Design at EPFL is acknowledged for providing
computational resources.
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