The Journal of Organic Chemistry
Article
Computational Details. All calculations were performed using the
Gaussian09 series of programs.22 Full quantum mechanics calculations
on model systems were performed within the framework of density
functional theory (DFT) using the B3LYP functional.23 The basis set
for all the atoms was the 6-31G(d,p) basis set.24 All geometry
optimizations were full, with no restrictions using the Berny algorithm
implemented in Gaussian09.25 All minima and transition states were
confirmed by performing frequency calculations. Transition states
were characterized by a single imaginary frequency, whose normal
mode corresponded to the expected motion. Because the qualitative
trends on selectivity are not affected by the polarity of the solvent (see
Tables 3 and 4), calculations were performed in vacuum. To confirm
this reasoning, we computed the solvent effects of toluene and
acetonitrile via the continuum IEF-PCM model26 for the amine
addition to the s-trans isomer of crotonaldehyde 1a. After the effects of
both solvents had been included, the energy differences between 1,2-
and 1,4-addition pathways remained qualitatively and quantitatively
similar to each other (+2.5 and +1.3 kcal mol−1 for toluene and
acetonitrile, respectively) and to in vacuum calculations (i.e., +4.4 kcal
mol−1). The natural bond orbital (NBO) method27 was used to
analyze the resultant wave function in terms of optimally chosen
localized orbitals, corresponding to a Lewis structure representation of
chemical bonding. In the case of some s-cis transition states, the
optimal Lewis structure was slightly modified to account for the
second-order perturbative donor−acceptor interaction between the Cα
lone pair and the π*CO orbital.
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ASSOCIATED CONTENT
Org. Biomol. Chem. 2012, 10, 1746. (b) Soule,
Kobayashi, S. Chem. Commun. 2013, 49, 355.
́
J.-F.; Miyamura, H.;
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S
* Supporting Information
(11) Carter, C. F.; Lange, H.; Ley, S. V.; Baxendale, I. R.; Wittkamp,
B.; Goode, J. G.; Gaunt, N. L. Org. Process Res. Dev. 2010, 14, 393.
(12) For information regarding additions to enones under kinetic or
thermodynamic control, see: Schultz, A. G.; Yee, Y. K. J. Org. Chem.
1976, 41, 4044.
General experimental details, ReactIR and NMR data, and DFT
calculation data and geometries. This material is available free
AUTHOR INFORMATION
(13) Brown, K. H. Ph.D. Thesis, Durham University, Durham, U.K.,
1999.
(14) (a) Benhallam, R.; Zair, T.; Jarid, A.; Ibrahim-Ouali, M. J. Mol.
Struct.: THEOCHEM 2003, 626, 1. (b) Benhallam, R.; Essaoudi, A.;
Zair, T. Phys. Chem. News 2002, 8, 110.
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Corresponding Authors
(15) See, for example: Romo, S.; Antonova, N. S.; Carbo,
J. M. Dalton Trans. 2008, 5166.
́
J. J.; Poblet,
Notes
The authors declare no competing financial interest.
(16) (a) Barba, C.; Carmona, D.; García, J. I.; Lamata, M. P.;
Mayoral, J. A.; Salvatella, L.; Viguri, F. J. Org. Chem. 2006, 71, 9831.
(b) Loncharich, R. J.; Brown, F. K.; Houk, K. N. J. Org. Chem. 1989,
54, 1129.
(17) Bokareva, O. S.; Bataev, V. A.; Godunov, I. A. J. Mol. Struct.:
THEOCHEM 2009, 913, 254.
(18) Durig, J. R.; Brown, S. C.; Kalasinsky, V. F.; George, W. O.
Spectrochim. Acta, Part A 1976, 32, 807.
(19) (a) Fantoni, A. C.; Caminati, W. Chem. Phys. Lett. 1987, 133, 27.
(b) During, J. R.; Little, T. S. J. Chem. Phys. 1981, 75, 3660. (c) Krantz,
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(20) Feringa, B. L.; Jansen, J. F. G. A. Synthesis 1988, 3, 184.
(21) For an example of ReactIR being used to follow low-
temperature lithiations, see: Campos, K. R.; Carbone, G.; Coldham,
I.; O’Brien, P.; Sanderson, A.; Stead, D. J. Am. Chem. Soc. 2010, 132,
7260.
(22) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.;
Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin,
K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
ACKNOWLEDGMENTS
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We thank the EPSRC for Doctoral Training Account funding
to A.D.J.C., the Ministerio de Ciencia e Innovacion
́
(MICINN)
of Spain (Projects CTQ2011-29054-C02-01 and CTQ2010-
16226), and the Direccio General de Recerca (DGR) of the
Autonomous Government of Catalonia (Grants 2009SGR462
and XRQTC).
́
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