Full Paper
c) L. El Ka¨ım, L. Grimaud, in Smiles Rearrangement: Rearrangements in
Synthesis (Ed.: C. M. Rojas), Wiley, 2013.
[5] a) N. Chꢀron, R. Ramozzi, L. El Kaim, L. Grimaud, P. Fleurat-Lessard, J.
theoretical calculations about Ugi mechanism, see: b) G. A. Medeiros,
W. A. da Silva, G. A. Bataglion, D. A. C. Ferreira, H. C. B. Oliveira, M. N.
[6] N. Chꢀron, R. Ramozzi, L. El Ka¨ım, L. Grimaud, P. Fleurat-Lessard, J. Phys.
Shinc, L. Y. Wang, J. Z. Zhou, H. B. Qiao, X. Tian, X. Y. Ma, H. Zuo, Synlett
2010, 2, 483–487.
[8] Gaussian 09 (RevisionA.02), M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.
Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Men-
nucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian,
A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara,
K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O.
Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro,
M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Ko-
bayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyen-
gar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,
O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin,
K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg,
S. Dapprich, A. D. Daniels, ꢄ. Farkas, J. B. Foresman, J. V. Ortiz, J. Cio-
slowski, D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
[10] a) W. Ren, E. Vanden-Eijnden, Phys. Rev. B 2002, 66, 052301; b) P. Fleurat-
Lessard, P. Dayal, A Chemist View on Reaction Path Determination, to be
sard/ReactionPath.html.
duced pressure to afford the crude Ugi–Smiles product. The latter
was purified by flash column chromatography on silica gel (petro-
leum ether/diethyl ether 85:15) to obtain the desired product as
an orange-brown oil (80%, 331 mg).
1H NMR (400 MHz, CDCl3): d=7.45–7.37 (m, 2H), 7.22 (d, J=8.3 Hz,
2H), 7.16–7.09 (m, 3H), 5.59–5.53 (m, 1H), 5.07(d, J=10.3 Hz, 1H),
5.06 (d, J=17.2 Hz, 1H), 4.39 (d, J=6.1 Hz, 2H), 3.77 (dd, J=8.8,
5.3 Hz, 1H), 3.72 (dd, J=15.3, 6.7 Hz, 1H), 3.41 (dd, J=15.3, 5.6 Hz,
1H), 2.35 (s, 3H), 1.83 (ddd, J=13.5, 8.8, 5.0 Hz, 1H), 1.67–1.56 (m,
1H), 1.40 (ddd, J=13.5, 8.4, 5.3 Hz, 1H), 0.83 (d, J=6.6 Hz, 3H),
0.80 ppm (d, J=6.6 Hz, 3H); 13C NMR (100.6 MHz, CDCl3): d=172.2,
146.0, 139.6, 136.9, 134.4, 133.5, 132.8, 129.1, 128.6, 125.2, 124.9,
118.8, 65.4, 52.9, 42.7, 38.6, 25.5, 23.1, 22.0, 20.5 ppm; IR: n˜bar
=
3390, 2959, 2923, 2878, 1660, 1527, 1493, 1357, 1280, 1224, 1172,
1095, 1018 cmꢀ1; HRMS: calcd for C23H28ClN3O2: 413.1870, found:
413.1878.
Other products and characterizations are detailed in Supporting In-
formation.
Acknowledgements
The authors thank ANR-08-CP2D-15-02, ENS de Lyon, ENSTA,
and CNRS for financial support. This work was granted access
to the HPC resources of IDRIS under the allocations 2012-
080609 and 2013-080609 made by GENCI (Grand Equipement
National de Calcul Intensif). This work has been achieved in
part by resources from PSMN (Pꢂle Scientifique de Modꢀlisa-
tion Numꢀrique). R.R. thanks the ENS de Cachan and N.C. the
ENS de Lyon for a fellowship.
Keywords: density functional calculations · multicomponent
reactions · nitrosophenols · prediction · Ugi–Smiles coupling
[11] a) S. Mierts, E. Scrocco, J. Tomasi, J. Chem. Phys. 1981, 55, 117–129;
b) N. Chꢀron, L. El Ka¨ım, L. Grimaud, P. Fleurat-Lessard, Chem. Eur. J.
Zhu, H. Bienaymꢀ), Wiley-VCH, Weinheim, 2005; e) A. Dçmling, Chem.
thesis and Material Science (Ed.: V. Nenadjenko), Wiley-VCH, Weinheim,
Received: January 27, 2014
[2] a) I. Ugi, R. Meyr, U. Fetzer, C. Steinbrꢃckner, Angew. Chem. 1959, 71,
Published online on && &&, 0000
&
&
Chem. Eur. J. 2014, 20, 1 – 7
6
ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!