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3.39 (dd,1H, JH: 3.6,14.0, –CHCH2Ph), 3.84 (s, 3H, –ArOCH3), 4.31 (dd,
1H, JH: 3.2,12.4, –NCHCOCH2–), 6.45–6.50 (m, 2H), 6.97–7.09 (m, 4H),
7.28–7.48(m, 6H),7.49–7.50(m, 2H);13CNMR(100 MHz,CDCl3, 25 ꢀC,
TMS):
d 37.78 (–CHCH2Ph), 55.87 (–ArOCH3), 66.54 (–NCHCOCH2–),
102.62, 110.12, 111.47, 127.65, 127.88, 128.42, 129.10, 129.24, 130.57,
132.88,135.47 (Aryl),158.98 (ArCHN–),162.65(Ar, quaternary),168.80
(Ar, quaternary), 170.91 (–CHCOO–). HMRS (EI): m/z calcd [Mþ1H]
386.1564, found [Mþ1H] 386.1571.
Compound 24 was obtained in 63% after 20 h at 90 ꢀC (0.095 g), 1H
NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
d 2.35 (s, 3H, –ArCH3), 2.70 (t,1H,
JH: 12.0, –CHCH2Ph), 3.41 (dd, 1H, JH: 2.0, 14.0, –CHCH2Ph), 4.34 (dd,
1H, JH: 4.0,12.0, –CHCH2Ph), 6.73 (d,1H, JH: 8.0 Hz), 6.85 (s,1H), 6.97–
7.03 (m, 3H), 7.12 (s, 1H), 7.28–7.38 (m, 6H), 7.45–7.47 (m, 2H); 13C
NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
d 22.50 (–ArCH3), 37.75(–
CHCH2Ph), 66.75(–NCHCOCH2–),115.41,120.38,121.74,127.74,127.88,
128.48, 129.14, 129.24, 130.58, 131.23, 135.28 (Aryl), 151.41 (Ar, qua-
ternary),159.95 (Ar, quaternary),159.99 (ArCHN–), 170.58 (–CHCOO–
). HMRS (EI): m/z calcd [Mþ1H] 370.1614, found [Mþ1H] 370.1615.
Compound 25 was obtained in 80% after 20 h at 90 ꢀC (0.122 g),
1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
d 2.68 (t, 1H, JH: 13.2,
–CHCH2Ph), 3.45 (dd, 1H, JH: 3.4, 13.8, –CHCH2Ph), 4.36 (dd, 1H, JH:
3.2, 12.4, –NCHCOCH2–), 6.80–7.71 (m, 14H); 13C NMR (100 MHz,
CDCl3, 25 ꢀC, TMS):
d 37.79 (–CHCH2Ph), 66.87 (–NCHCOCH2–),
114.74, 114.94, 117.47, 120.32, 120.38, 127.91, 129.16, 129.24,
131.53,132.34, 132.41, 134.97, 139.23 (Aryl), 159.84 (Ar, quaternary),
160.56 (Ar, quaternary), 170.13 (–CHCOO–). HMRS (EI): m/z calcd
[Mþ1H] 374.1364, found [Mþ1H] 374.1367.
12. (a) Wang, Q.; Finn, M. G. Org. Lett. 2000, 2, 4063–4065; (b) Petasis, N. A.;
Butkevich, A. N. J. Organomet. Chem. 2009, 694, 1747–1753.
13. Portlock, D. E.; Naskar, D.; West, L.; Li, M. Tetrahedron Lett. 2002, 43, 6845–6847.
´
F.; Debache, A.; Marsac, Y.; Collet, B.; Girard-Le Bleiz, P.; Carboni, B.
14. Berree,
Compound 26 was obtained in 31% after 20 h at 90 ꢀC (0.048 g),
Tetrahedron 2006, 62, 4027–4037.
1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
d 2.72 (t, 1H, JH: 13.0,
15. Regnier, T.; Berree, F.; Lavastre, O.; Carboni, B. Green Chem. 2007, 9, 125–126.
16. Selected examples: (a) Barba, V.; Rodrı´guez, A.; Ochoa, M. E.; Santillan, R.;
Farfa´n, N. Inorg. Chim Acta 2004, 357, 2593–2601; (b) Abreu, A.; Alas, S. J.;
Beltra´n, H. I.; Santillan, R.; Farfa´n, N. J. Organomet. Chem. 2006, 691, 337–348; (c)
Braun, M.; Schlecht, S. M.; Engelmann, M.; Frank, W. Eur. J. Org. Chem. 2008,
5221–5225; (d) Kaiser, P. F.; White, J. M.; Hutton, C. A. J. Am. Chem. Soc. 2008,
130, 16450–16451; (e) Christinat, N.; Croisier, E.; Scopelliti, R.; Cascella, M.;
Ro¨thlisberger, U.; Severin, K. Eur. J. Inorg. Chem. 2007, 5177–5181; (f) Christinat,
N.; Scopelliti, R.; Severin, K. J. Org. Chem. 2007, 72, 2192–2200; (g) Christinat, N.;
Scopelliti, R.; Severin, K. Angew. Chem., Int. Ed. 2008, 47, 1848–1852; (h) Farfa´n,
–CHCH2Ph), 3.42 (dd, 1H, JH: 3.2, 13.6, –CHCH2Ph), 3.81 (s, 3H,
–ArOCH3), 4.34 (dd, 1H, JH: 3.2, 12.4, –NCHCOCH2–), 6.80–7.35 (m,
14H); 13C NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
d 37.87 (–CHCH2Ph),
55.04 (–ArOCH3), 66.82 (–NCHCOCH2–), 113.42, 117.55, 120.15,
120.27, 127.80, 129.16, 129.28, 131.48, 131.96, 135.14, 138,92 (Ph),
159.94 (ArCHN–), 159.98, 160.22 (Ar, quaternary), 170.42 (–CHCOO–
). HMRS (EI): m/z calcd [Mþ1H] 386.1564, found [Mþ1H] 386.1556.
Compound 27 was obtained in 83% after 20 h at 90 ꢀC (0.126 g),
´
´
N.; Ho¨pfl, H.; Barba, V.; Ochoa, M. E.; Santillan, R.; Gomez, E.; Gutierrez, A.
J. Organomet. Chem. 1999, 581, 70–81.
1H NMR (400 MHz, CDCl3, 25 ꢀC, TMS):
d 2.34 (s, 3H, –ArCH3), 2.73
´
´
17. Beltran, H. I.; Zamudio-Rivera, L. S.; Mancilla, T.; Santillan, R.; Farfan, N. J. Or-
ganomet. Chem 2002, 657, 194–204.
(t, 1H, JH: 12.0, –CHCH2Ph), 3.42 (dd, 1H, JH: 4.0, 14.0, –CHCH2Ph),
4.35 (dd, 1H, JH: 4.0, 12.0, –NCHCOCH2–), 6.91 (t, 1H, JH: 8.0), 6.99–
7.04 (m, 3H), 7.12–7.16 (m, 4H), 7.28–7.38 (m, 5H), 7.50–7.56 (m,
18. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford
University Press: New York, 1989.
19. (a) Wiberg, K. B. Tetrahedron 1968, 24, 1083–1096; (b) Wiberg indices are
electronic parameters related to the electron density between atoms. They can
be obtained from a Natural Population Analysis and provide an indication of
the bond strength.
20. (a) Carpenter, J. E.; Weinhold, F. J. Mol. Struct. (Theochem) 1988, 169, 41–62; (b)
Carpenter, J.E. PhD Thesis, University of Wisconsin (Madison WI), 1987. (c)
Foster, J. P.; Weinhold, F. J. Am. Chem. Soc. 1980, 102 7211–7118; (d) Reed, A. E.;
Weinhold, F. J. Chem. Phys. 1983, 78, 4066–4073; (e) Reed, A. E.; Weinhold, F. J.
Chem. Phys. 1985, 78, 1736–1740; (f) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J.
Chem. Phys. 1985, 83, 735–746; (g) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem.
Rev. 1988, 88, 899–926; (h) Weinhold, F.; Carpenter, J. E. The Structure of Small
Molecules and Ions; Plenum: New York, 1988; p. 227.
1H); 13C NMR (100 MHz, CDCl3, 25 ꢀC, TMS):
d 21.44 (–ArCH3), 37.78
(–CHCH2Ph), 66.90 (–NCHCOCH2–), 117.62, 120.14, 120.32, 127.80,
128.67, 129.16, 129.28, 130.61, 131.46, 135.21, 138.19, 138.94 (Aryl),
159.94 (Ar, quaternary), 160.35 (ArCHN–), 170.35 (–CHCOO–).
HMRS (EI): m/z calcd [Mþ1H] 370.1614, found [Mþ1H] 370.1620.
Acknowledgements
ˆ
We thank the Fundaça˜o para a Ciencia e Tecnologia (POCI 2010)
21. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.;
Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.;
Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.;
Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J.
V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.;
Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-
Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.;
Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Re-
vision C.02; Gaussian: Wallingford CT, 2004.
and FEDER (SFRH/BPD/46589/2008, PTDC/QUI/66695/2006, PTDC/
QUI/66015/2006, POCI/QUI/60175/2004, POCI/QUI/58791/2004) for
financial support.
Supplementary data
Supplementary data associated with this article can be found, in
References and notes
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