G. Ren et al. / Tetrahedron 66 (2010) 4022e4028
4027
(400 MHz, CDCl3)
7.20e7.17 (m, 1H), 6.94e6.86 (m, 2H), 6.78e6.72 (m, 1H); 13C NMR
(100 MHz, CDCl3) 143.1, 142.2, 139.7, 137.4, 133.8, 130.6, 128.5,
d
7.45e7.36 (m, 3H), 7.32e7.24 (m, 11H),
Supplementary data
d
Supplementary data associated with this article can be found in
128.24, 128.22, 128.20, 127.6, 127.5, 127.4, 127.1, 126.4.
4.2.24. t e r t -Butyl-4-(4-styrylphenyl)piperazine-1-carboxylate
References and notes
(3x). Light yellow solid, mp 176e178 ꢀC; 1H NMR (400 MHz, CDCl3)
d
7.48 (d, J¼7.8 Hz, 2H), 7.44 (d, J¼8.7 Hz, 2H), 7.36e7.32 (m, 2H),
1. (a) Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jpn. 1971, 44, 581; (b) Heck,
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7.24e7.20 (m, 1H), 7.07e6.95 (m, 2H), 6.91 (d, J¼8.5 Hz, 2H),
3.60e3.58 (m, 4H), 3.18e3.16 (m, 4H), 1.49 (s, 9H); 13C NMR
(100 MHz, CDCl3)
d 154.7, 137.7, 128.6, 128.2, 127.5, 127.1, 126.2,
3. For examples, see: (a) Bader, R. R.; Baumeister, P.; Blaser, H. U. Chimia 1996, 50,
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Vries, J. G. Can. J. Chem. 2001, 79, 1086.
126.1, 116.3, 80.0, 49.0, 28.4; HRMS (positive ESI) calcd for
C23H28N2O2 [MþH]þ: 365.2229, found: 365.2228.
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4.3. Procedure of kinetic experiments
The parallel experiments were performed using PhBr
(0.5 mmol), ethyl acrylate (0.75 mmol), K3PO4 (1.0 mmol), TBAB
(0.5 mmol), and complex 1 or dimer 2 (0.001 mmol) in DMF (5 mL).
The reactions were monitored by GC.
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4.4. 13C NMR experiments
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4.4.1. Procedure for preparation of imine 4 (Scheme 2). 13C-enriched
hypnone (13C-enriched in benzene) was prepared from 13C-ben-
zene by FriedeleCrafts acylation reaction. Then a mixture of 13C-
enriched hypnone (13C-enriched in benzene) (2.0 mmol) and
4-methoxyaniline (2.01 mmol) was dissolved in 30 mL of dry tol-
uene and refluxed under nitrogen atmosphere in the presence of
8. (a) Usón, R.; Forniés, J.; Navarro, R. J. Organomet. Chem. 1975, 96, 307; (b) Usón,
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ꢀ
molecular sieves (4 A, 1.5 g). After 4 h, the reaction mixture was
carefully filtered and the filtrate was reduced to dryness. The imine
4 was re-crystallized from cold CH3OH (yield 86%, yellow solid).
HRMS (positive ESI) calcd for C913C6H15NO [MþH]þ: 232.1388,
found: 232.1392.
ꢁ
10. Sjovall, S.; Wendt, O. F.; Andersson, C. J. Chem. Soc., Dalton Trans. 2002, 1396.
11. (a) Hermann, W. A.; Bohm, V. P. W.; Reisinger, C. P. J. Organomet. Chem. 1999,
576, 23; (b) Rosner, T.; Le Bars, J.; Pfaltz, A.; Blackmond, D. G. J. Am. Chem. Soc.
2001, 123, 1848; (c) Rosner, T.; Pfaltz, A.; Blackmond, D. G. J. Am. Chem. Soc. 2001,
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Hermann, W. A. Chem.dEur. J. 2001, 7, 4191; (f) Bedford, R. B.; Hazelwood, S. L.;
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4.4.2. Procedure for preparation of palladacycle 5. A solution of
Li2PdCl4 in methanol (10 mL) was added to a solution of 1 equiv of
NaOAc and imine 4. The mixture was stirred at room temperature
for 24 h, then filtrated and re-crystallized from CH3OH. Palladacycle
5 (yellow solid) was obtained in 78% yield. HRMS (positive ESI)
13
calcd for C18
742.0008.
C
H28Cl2N2O2Pd2 [MꢁCl]þ: 742.0000, found:
12
4.4.3. Procedure of 13C NMR experiments. A solution of ethyl acry-
late (0.024 mmol), 2-bromonitrobenzene (0.02 mmol), Et3N
12. Beletskaya, I. P.; Kashin, A. N.; Karlstedt, N. B.; Mitin, A. V.; Cheprakov, A. V.;
Kazankov, G. M. J. Organomet. Chem. 2001, 622, 89.
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J. Y.; Cui, M. J.; Yu, A. J.; Wu, Y. J. J. Organomet. Chem. 2007, 692, 3732; (c) Ma, J.;
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Ren, G. R.; Cui, X. L; Wu, Y. J Eur. J. Org. Chem. 2010, 2010, 2372.
(0.03 mmol), and palladacycle 5 (0.02 mmol) in DMF (400 mL) were
13
monitored by C NMR when ꢁ60 ꢀC, 25 ꢀC, 50 ꢀC, 80 ꢀC, and
140 ꢀC, respectively.
4.5. Procedure of Hg poisoning experiments
15. (a) Reardon, P.; Metts, S.; Crittendon, C.; Daugherity, P.; Parsons, E. J. Organome-
tallics 1995, 14, 3810; (b) Iyer, S.; Raimesh, C.; Ramani, A. Tetrahedron Lett.1997, 38,
8533; (c) Berthiol, F.; Doucet, H.; Santelli, M. Synlett 2003, 841; (d) Lemhadri, M.;
Battace, A.; Berthiol, F.; Zair, T.; Doucet, H.; Santelli, M. Synthesis 2008, 1142.
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1994, 483, 139.
17. Arduengo, A. J., III; Krafczyk, R.; Schmutzler, R. Tetrahedron 1999, 55, 14523.
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An excess (300 equiv to the palladacycle) of Hg(0) was added
into the reaction mixture of PhBr (0.5 mmol), ethyl acrylate
(0.75 mmol), K3PO4 (1.0 mmol), TBAB (0.5 mmol), and complex 1
(0.001 mmol) in DMF (5 mL) at t¼0, 0.5 h, respectively.
An excess (300 equiv to the palladacycle) of Hg(0) was added
into the reaction mixture of PhBr (0.5 mmol), ethyl acrylate
(0.75 mmol), K3PO4 (1.0 mmol), TBAB (0.5 mmol), and dimer 2
(0.001 mmol) in DMF (5 mL) at t¼0, 7.5 h, respectively.
21. Chen, Y.; Huang, L. Y.; Ranade, M. A.; Zhang, X. P. J. Org. Chem. 2003, 68, 3714.
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Acknowledgements
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We are grateful to the NSF of China (20772114), NSF of Henan
(082300423201) for the financial support to this research.