Highly Efficient Catalytic Dimerization of Styrenes via Cationic Palladium(II) Complexes
1
1
,3-Di(4-chlorophenyl)but-1-ene:
H NMR (300 MHz,
pounds, (Eds.: B. Cornils, W. A. Herrmann), VCH,
New York, 1996, Vol. 2, pp. 1024.
CDCl ): d=7.28–7.14 (m, 8H), 6.35–6.23 (m, 2H), 3.62–3.53
m, 1H), 1.42–1.40 (d, J=6 Hz, 3H); C NMR (75 MHz,
CDCl ): d=143.8, 135.9, 135.4, 132.8, 132.1, 128.8, 128.7,
27.9, 127.5, 42.0, 21.2; GC/MS (EI): m/z=276 (M ).
Mixture of a and b from Co-dimerization of a-Methylstyr-
ene (NMR ratio=1:0.8 based on olefinic-H): H NMR
300 MHz, CDCl ): d=7.51–7.31 (m, 10H), 6.28 (s, olefinic
3
1
3
[
6] For Co-catalyzed dimerizations, see a) L. Pu, A. Yama-
moto, S. Ikeda, J. Am. Chem. Soc. 1968, 90, 7170;
b) M. M. P. Grutters, C. Mꢃller, D. Vogt, J. Am. Chem.
Soc. 2006, 128, 7414; c) R. K. Sharma, T. V. RajanBabu,
J. Am. Chem. Soc. 2010, 132, 3295; d) D. Vogt, Angew.
Chem. 2010, 122, 7323; Angew. Chem. Int. Ed. 2010, 49,
7166; e) M. M. P. Grutters, J. I. van der Vlugt, Y. X. Pei,
A. M. Mills, M. Lutz, A. L. Spek, C. Muller, C.
Moberg, D. Vogt, Adv. Synth. Catal. 2009, 351, 2199;
f) J. P. Page, T. V. RajanBabu, J. Am. Chem. Soc. 2012,
(
3
+
1
1
(
3
1
34, 6556.
[
7] For Pd-catalyzed hydrovinylations, see a) U. Englert,
R. Haerter, D. Vasen, A. Salzer, E. B. Eggeling, D.
Vogt, Organometallics 1999, 18, 4390; b) J. Albert, M.
Cadena, J. Granell, G. Muller, J. I. Ordinas, D. Panyel-
la, C. Puerta, C. Sanudo, P. Valerga, Organometallics
1999, 18, 3511.
H of a, 1H), 5.29 (s, olefinic H of b, 1H), 4.93 (s, olefinic H
of b, 1H), 2.98 (s, CH of b, 2H), 1.71 (s, CH of b, 3H).,
2
3
1
3
1
.66 [s, (CH ) of b, 6H], 1.37 [s, (CH ) of a, 6H]; C NMR
3
2
3
2
(
75 MHz, CDCl ): d=151.6, 150.6, 149.5, 149.1, 146.8, 145.0,
[8] C. R. Smith, T. V. RajanBabu, J. Org. Chem. 2009, 74,
3066.
3
1
1
3
42.5, 141.0, 138.9, 137.8, 136.4, 128.3, 128.2, 127.9, 126.6,
26.3, 126.0, 125.9, 117.0, 49.7, 40.3, 40.2, 39.3, 38.8, 38.1,
[9] a) D. J. Mans, G. A. Cox, T. V. RajanBabu, J. Am.
Chem. Soc. 2011, 133, 5776; b) H. J. Lim, T. V. Rajan-
Babu, Org. Lett. 2011, 13, 6596; c) W. Liu, H. J. Lim,
T. V. RajanBabu, J. Am. Chem. Soc. 2012, 134, 5496.
10] a) D. W. Stephan, A. J. Hoskin, Coord. Chem. Rev.
+
1.2, 29.6, 29.1, 17.3; MS (EI): m/z=236 (M ).
[
[
2
002, 233–234, 107; b) D. W. Lee, C. S. Yi, Organome-
Acknowledgements
tallics 2010, 29, 3413.
11] For Ni(II)-catalyzed styrene dimerization, oligomeriza-
tion and/or polymerization, see a) M. Jimꢄnez-Tenorio,
M. C. Puerta, I. Salcedo, P. Valerga, D. I. Costa, L. C.
Silva, P. T. Gomes, Organometallics 2004, 23, 3139;
b) D. Gareau, C. Sui-Seng, L. F. Groux, F. Brisse, D.
Zargarian, Organometallics 2005, 24, 4003; c) M. Jimꢄ-
nez-Tenorio, M. C. Puerta, I. Salcedo, P. Valerga,
I. D. L. Rios, K. Mereiter, Dalton Trans. 2009, 1842;
d) L. B. Junquera, C. Puerta, P. Valerga, Organometal-
lics 2012, 31, 2175.
12] For Pd-catalyzed styrene dimerization, see a) A. Sen,
T.-W. Lai, Organometallics 1983, 2, 1059; b) A. Sen, Z.
Jiang, Organometallics 1993, 12, 1406; c) T. Tsuchimo-
to, S. Kamiyama, R. Negoro, E. Shirakawa, Y. Kawaka-
mi, Chem. Commun. 2003, 852; d) J. P. Peng, J. Li, H.
Qiu, J. Jiang, K. Jiang, J. Mao, G. Lai, J. Mol. Catal. A:
Chemical 2006, 255, 16; e) V. S. Tkach, D. S. Suslov, G.
Myagmarsuren, G. V. Ratovskii, A. V. Rohin, T. Felix,
F. K. Shmidt, J. Organomet. Chem. 2008, 693, 2069;
f) L. Fanofi, A. Meduri, E. Zangrando, S. Castillon, F.
Felluga, B. Milani, Molecules 2011, 16, 1804; g) G.
Myagmarsuren, V. S. Tkach, F. K. Shmidt, M. Mo-
hamed, D. S. Suslov, J. Mol. Catal. A: Chemical 2005,
235, 154; h) V. S. Tkach, G. Myagmarsuren, D. S.
Suslov, M. Mesyef, F. K. Shmidt, Catal. Commun. 2007,
8, 677; i) D. S. Suslov, V. S. Thach, M. V. Bykov, M. V.
Belova, Petrol. Chem. 2011, 51, 169.
Financial supports provided by the KRICT (SI-1304) and the
US NSF (CHE 1057818) are gratefully acknowledged.
References
[1] a) S. M. Pillai, M. Ravindranathan, S. Sivaram, Chem.
Rev. 1986, 86, 353; b) J. Skupinska, Chem. Rev. 1991,
9
3
1, 613; c) S. Mecking, Coord. Chem. Rev. 2000, 203,
25; d) F. Speiser, P. Braunstein, L. Saussine, Acc.
[
Chem. Res. 2005, 38, 784.
2] a) H. Olivier-Bourbigou, L. Saussine, in: Applied Ho-
[
mogeneous Catalysis with Organometallic Compounds,
nd
2
edn., (Eds.: B. Cornils, W. A. Herrmann), Wiley-
VCH, Weinheim, 2002; Vol. 1; b) W. Keim, Angew.
Chem. 1990, 102, 251; Angew. Chem. Int. Ed. Engl.
1
990, 29, 235.
[
3] a) W. Keim, A. Behr, M. Rçper, in: Comprehensive Or-
ganometallic Chemistry, (Eds.: G.Wilkinson, F. G. A.
Stone, E. W. Abel), Pergamon Press, New York, 1982;
Vol. 12; b) S. Datta, M. B. Fischer, S. S. Wreford, J. Or-
ganomet. Chem. 1980, 188, 353; c) R. Schrock, S.
McLain, J. Sancho, Pure Appl. Chem. 1980, 52, 729;
d) C. Andes, S. B. Harkins, S. Murtuza, K. Oyler, A.
Sen, J. Am. Chem. Soc. 2001, 123, 7423; e) Z.-X. Yu,
K. N. Houk, Angew. Chem. 2003, 115, 832; Angew.
Chem. Int. Ed. 2003, 42, 808.
[13] a) M. G. Barlow, M. J. Bryant, R. N. Hagzeldine, A. G.
Mackie, J. Organomet. Chem. 1970, 21, 215; b) G.
Wilke, Ger. Offen. 1,520,964, 1974; c) S. Hattori, H.
Munakata, K. Tatauoka, T. Shimizu, Ger. Offen.
2,234,922, 1974, U.S. Patent 3,803,254, 1974.
[4] A. M. Trzeciak, J. J. Ziolkowski, Coord. Chem. Rev.
2
005, 249, 2308.
[
5] For reviews, see a) T. V. RajanBabu, Synlett 2009, 853;
b) T. V. RajanBabu, Chem. Rev. 2003, 103, 2845;
c) P. W. Jolly, G. Wilke, Hydrovinylation, in: Applied
Homogeneous Catalysis with Organometallic Com-
[14] H. J. Lim, C. R. Smith, T. V. RajanBabu, J. Org. Chem.
2009, 74, 4565.
Adv. Synth. Catal. 2013, 355, 3633 – 3638
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