Efficient and selective nickel(II)-catalyzed tail-to-head dimerization of styrenes affording 1,3-diaryl-1-butenes

doi:10.1016/j.catcom.2007.04.010

Catalysis Communications

Volume 9, Issue 1, January 2008, Pages 85-88

https://doi.org/10.1016/j.catcom.2007.04.010 Get rights and content

Abstract

NiCl₂(dppp) [dppp = 1,3-bis(diphenylphosphino)propane] shows high catalytic activity for the head-to-tail dimerization of styrene and its derivatives bearing electron-donating or electron-withdrawing groups. The dimerization proceeds with high regio- and stereoselectivity to afford trans-1,3-diaryl-1-butenes in high yields.

Introduction

Catalytic carbon–hydrogen bond activation followed by carbon–carbon bond formation is an important class of reaction in organic synthesis [1]. Homo- [2] and heterodimerization [3] of olefins is one of the most important topics in this area, and a number of efficient catalyst systems have been reported for such reactions, particularly in asymmetric heterodimerization [4].

Recently, we have been interested in the synthesis of the conjugated molecule of 1,3-diaryl-1,3-butadienes, and designed a synthetic route in which the key intermediate is the simple 1,3-diaryl-1-butenes (Scheme 1). Although Dawans reported that [Ni(π-C₃H₅)(OCOCF₃)]₂ could catalyze dimerization of styrenes to afford 1,3-diaryl-1-butene in moderate selectivity [5], Shirakawa [2g] and Cheng [2h] have recently reported that the catalyst systems of Pd(OAc)₂ (1 mol.%)/PPh₃ (1 mol.%)/In(OTf)₃ (5 mol.%) and CoX₂(PPh₃)₃ (10 mol.%)/PPh₃ (30 mol.%)/Zn (1.5 equiv.) showed high catalytic activity for the same dimerization reaction, we hope to develop a more simple and efficient catalyst system for such type of dimerization. In this paper, we report our new findings of Ni(dppp)Cl₂-catalyzed selective tail-to-head dimerization of styrenes to give 1,3-diaryl-1-butenes in good to high yield (Scheme 2).

Section snippets

Results and discussion

Table 1 shows the results from the dimerization of styrene (1a) under different reaction conditions using toluene as solvent in a sealed tube for 24 h. We first examined the catalytic activity of the mixture of the simple nickel(II) halides with phosphine ligands in the presence of Bu₃N. We have found that NiCl₂/dppb (1:1 in molar ratio) [dppb = 1,4-bis(diphenylphospino)butane], NiCl₂/dppp (1:1 in molar ratio) and NiBr₂/dppp (1:1 in molar ratio) showed moderate catalytic activity for the formation

Conclusion

In conclusion, a convenient and efficient procedure for the synthesis of trans-1,3-diaryl-1-butenes has been developed through the regio- and stereoselective tail-to-head dimerization of styrenes in the presence of Ni(dppp)Cl₂.

General

All organic starting materials were analytically pure and used without further purification. ¹H and ¹³C NMR spectra were recorded on a JOEL JNM-ECA300 spectrometer at 300 MHz and 75 MHz, respectively. Mass spectra were obtained on a HEWLETT 5890 PACKARD SERIES II GC/MS spectrometer with a PEG-25M column. GC analyses of organic compounds were performed on an Agilent Technologies 1790 GC (with a TC-WAX capillary 25 m column) instrument. Element analyses were obtained with a Flash EA 1112 Element

Acknowledgement

This project (20590360) was supported by National Natural Science Foundation of China.

References (10)

T.-Y. Luh et al.
Chem. Rev.
(2000)
C.S. Chin et al.
Acc. Chem. Res.
(2002)
K. Fagnou et al.
Chem. Rev.
(2003)
D. Prajapati et al.
Tetrahedron
(2004)
M. Shibasaki et al.
Adv. Synth. Catal.
(2004)
C.-J. Li
Chem. Rev.
(2005)
S.J. McLain et al.
J. Am. Chem. Soc.
(1978)
J. Christoffers et al.
J. Am. Chem. Soc.
(1996)
C.S. Yi et al.
J. Organomet. Chem.
(1998)
W.P. Kretschmer et al.
Organometallics
(1998)
S.A. Svejda et al.
Organometallics
(1999)
B.L. Small et al.
Organometallics
(2001)
T. Tsuchimoto et al.
Chem. Comm.
(2003)
C.-C. Wang et al.
Tetrahedron Lett.
(2004)
B.L. Small et al.
Chem. Eur. J.
(2004)
J. Jin et al.
Tetrahedron
(2000)
V. Fassina et al.
Tetrahedron
(2000)
C.S. Yi et al.
Organometallics
(2001)
B.M. Arciniec et al.
Organometallics
(2002)
N. Nomura et al.
J. Am. Chem. Soc.
(1998)
R.D. Broene et al.
J. Am. Chem. Soc.
(2005)
L.J. Gooßen
Angew. Chem., Int. Ed.
(2002)
G. Francio et al.
J. Am. Chem. Soc.
(2002)
T.V. RajanBabu
Chem. Rev.
(2003)
T.V. RajanBabu et al.
J. Org. Chem.
(2003)
R. Kumareswaran et al.
Org. Lett.
(2003)
A. Zhang et al.
Org. Lett.
(2004)
A. Grabulosa et al.
Organometallics
(2005)
W.-J. Shi et al.
Tetrahedron: Asymm.
(2005)
W.-J. Shi et al.
J. Am. Chem. Soc.
(2006)
H. Park et al.
Tetrahedron
(2005)
A. Zhang et al.
J. Am. Chem. Soc.
(2006)
L.-I. Rodriguez et al.
Organometallics
(2006)
F. Dawans
Tetrahedron Lett.
(1971)

There are more references available in the full text version of this article.

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Efficient and selective nickel(II)-catalyzed tail-to-head dimerization of styrenes affording 1,3-diaryl-1-butenes

Abstract

Introduction

Section snippets

Results and discussion

Conclusion

General

Acknowledgement

Chem. Rev.

Acc. Chem. Res.

Chem. Rev.

Tetrahedron

Adv. Synth. Catal.

Chem. Rev.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Organomet. Chem.

Organometallics

Organometallics

Organometallics

Chem. Comm.

Tetrahedron Lett.

Chem. Eur. J.

Tetrahedron

Tetrahedron

Organometallics

Organometallics

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Angew. Chem., Int. Ed.

J. Am. Chem. Soc.

Chem. Rev.

J. Org. Chem.

Org. Lett.

Org. Lett.

Organometallics

Tetrahedron: Asymm.

J. Am. Chem. Soc.

Tetrahedron

J. Am. Chem. Soc.

Organometallics

Tetrahedron Lett.