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therein. (i) Hoffmann, R.; Schleyer, P. v. R.; Schaefer, H. F. Angew. Chem., Int. Ed. 2008, 47, 7164–7167 (also see the comments of G. Frenking, W.
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(5) (a) Zhao, Y.; Truhlar, D. G. Theor. Chem. Account 2008, 120, 215–241. (b) Zhao, Y.; Truhlar, D. G. Acc. Chem. Res. 2008, 41, 157–167.
(6) (a) Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618–622. (b) Head-Gordon, M.; Pople, J. A.; Frisch, M. J. Chem. Phys. Lett. 1988, 153, 503–506.
(7) (a) Grimme, S. J. Comput. Chem. 2006, 27, 1787–1799. Also see references contained in the following reviews: (b) Johnson, E. R.; Mackie,
I. D.; Di Labio, G. A. J. Phys. Org. Chem. 2009, 22, 1127–1135. (c) Grimme, S. WIREs Comput. Mol. Sci. 2011, 1, 211–228. (d) Ehrlich, S.;
Moellmann, J.; Grimme, S. Acc. Chem. Res. 2013, 46, 916–926. (e) Corminboeuf, C. Acc. Chem. Res. 2014, 47, 3217–3224. (f) Cho, Y.; Cho, W.
J.; Youn, I. S.; Lee, G.; Singh, N. J.; Kim, K. S. Acc. Chem. Res. 2014, 47, 3321–3330. For a general review on non-covalent interactions (WFT and
DFT), see: (g) Riley, K. E.; Pitonak, M.; Jurecka, P.; Hobza, P. Chem. Rev. 2010, 110, 5023–5063 and references therein.
(8) ORCA 3.0.2. (a) Neese, F. The ORCA program system, Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2012, 2, 73–78. (b) Neese, F.;
Wennmohs, F.; et al., Max-Planck-Institut für Chemische Energiekonversion, Mülheim (www.cec.mpg.de).
(10) For example: (a) Cybulski, S. M.; Lytle, M. L. J. Chem. Phys. 2007, 127, 141102/1–141102/4. (b) Hesselmann, A. J. Chem. Phys. 2008,
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(11) For example: (a) Carneros, H.; Sánchez, D.; Vilarrasa, J. Org. Lett. 2014, 16, 2900–2903 (transfer of alkenyl groups between secondary
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(12) Seebach, D.; Yoshinari, T.; Beck, A. K.; Ebert, M.-O.; Castro-Alvarez, A.; Vilarrasa, J.; Reiher, M. Helv. Chim. Acta 2014, 97, 1177–1203.
(13) For the sake of simplicity, in this Scheme the ball depicted at position 2 of the pyrrolidine ring may be a hydrogen atom or any substituent
other than a COOH group (which has a strong tendency to form oxazolidinone rings or, in very polar media, zwitterionic iminium carboxylates) or
similar groups. Moreover, R3CCHO means not only pivalaldehyde and similar branched aliphatic aldehydes but also ArCHO and RCH=CHCHO; in
the presence of PhCOOH or other suitable acids as additives, the iminium hydroxide depicted in the second row of Scheme 1, also for simplicity,
must be replaced by the corresponding iminium carboxylates (plus water), as expected.
(14) The twist-boat conformer of ketone 2 is drawn in Table 1. It is predicted to be 2–3 kcal/mol more stable than the chair conformer, at all levels.
(15) (a) Marenich, A. V; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378–6396. (b) The SMD, CPCM, and IEFPCM approaches
were compared for this case (1a + 2 = 1 + 2a) at the B3LYP/6-31G(d) level, and the predicted ∆G˚(DMSO) values were –3.9, –4.6, and –4.6 kcal/mol,
respectively. (c) The SMD, CPCM, and IEFPCM approaches were also compared for other equilibria; for example, for the 5 + a = 5a + H2O
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