Page 3 of 5
Dalton Transactions
DOI: 10.1039/C3DT51674A
reduced by Zn powder to give possible intermediates 4.17 The
complex 4 can quickly react with two equivalents of alkyne to
give metallacyclopentadienes 5. In some cases of the reaction, a
trace amount of 1,4ꢀdiphenylbutaꢀ1,3ꢀdiene was detected. That
result confirmed that di(αꢀaryl)ꢀferrocyclopentadiene 5 would be
favoured over than (αꢀaryl)ꢀ(βꢀaryl) ones. The intermediate 5 can
further be cyclized to 6 and/or 7 through an insertion or [4+2]ꢀ
cycloaddition pathway, respectively. Reductive elimination
reaction of 6 and/or 7 yields benzene derivative 2 and regenerates
4 (a) R. L. Halterman, N. H. Nguyen and K. P. C. Vollhardt, J. Am.
Chem. Soc. 1985, 107, 1379; (b) R. Grigg, R. Scott and P. Stevenson,
Tetrahedron Lett. 1982, 23, 2691.
5 J. Li, H. Jiang and M. Chen, J. Org. Chem. 2001, 66, 3627.
50 6 (a) K. Tanaka, K. Shirasaka, Org. Lett. 2003, 5, 4697; (b) K. Yoshida,
I. Morimoto, K. Mitsudo and H. Tanaka, Tetrahedron, 2008, 64,
5800.
5
7 R. Takeuchi, Y. Nakaya, Org. Lett. 2003, 5, 3659.
8
(a) Y. Yamamoto, J. Ishii, H. Nishiyama and K. Itoh, J. Am. Chem.
Soc. 2004, 126, 3712. (b) M. Kawatsura, M. Yamamoto, J. Namioka,
K. Kajita, T. Hirakawa and T. Itoh, Org. Lett. 2011, 13, 1001.
55
9 (a) G. Hilt, T. Vogler, W. Hess and F. Galbiati, Chem. Commun. 2005,
1474; (b) N. Saino, F. Amemiya, E. Tanabe, K. Kase and S.
Okamoto, Org. Lett. 2006, 8, 1439; (c) M. Lombardo, F. Pasi, C.
Trombini, K. R. Seddon and W. R. Pitner, Green Chem. 2007, 9 321;
(d) L. Xu, R. Yu, Y. Wang, J. Chen and Z. Yang, J. Org. Chem.
2013, 78, 5744.
10 the low valent complex 4.
60
10 (a) H. Tsuji, K. Yamagata, T. Fujimoto and E. Nakamura, J. Am.
Chem. Soc. 2008, 130, 7792; (b) T. Takahashi, Z. Xi, A. Yamazaki,
Y. Liu, K. Nakajima and M. Kotora, J. Am. Chem. Soc. 1998, 120,
1672; (c) D. Suzuki, H. Urabe and F. Sato, J. Am. Chem. Soc. 2001,
123, 7925; (d) Y. Liu, X. Yan, N. Yang and C. Xi, Catal. Commun.
2011, 12, 489; (e) Y.ꢀl. Xu, Y.ꢀm. Pan, Q. Wu, H.ꢀs. Wang and P.ꢀz.
Liu, J. Org. Chem. 2011, 76, 8472. (f) X. Bu, Z. Zhang and X. Zhou,
Organometallics, 2010, 29, 3530; (g) Z. Zhu, C Wang, X. Xiang, C.
Pi and X. Zhou, Chem.Commun., 2006, 2066.
65
70
11 Examples for cyclomerization of alkynes, see: (a) Z. Qiu and Z. Xie,
Angew. Chem. Int. Ed. 2009, 48, 5729; (b) T. Iwayama and Y. Sato
Chem. Commun. 2009, 5245; (c) J. Louie, J. E. Gibby, M. V.
Farnworth and T. N. Tekavec, J. Am. Chem. Soc. 2002, 124, 15188;
(d) M. Shanmugasundaram, M.ꢀS. Wu and C.ꢀH. Cheng, Org. Lett.
2001, 3, 4233; (e) N. Mori, SꢀI Ikeda and K. Odashima, Chem.
Commun., 2001, 181.
12 Examples for crossing coupling reaction, see: for, (a) I. P. Beletskaya,
and A. V. Cheprakov, Chem. Rev. 2000, 100, 3009; (b) L. Wang, P.
Li and Y. Zhang, Chem. Commun. 2004, 514; (c) S. Kang, H. Ryu
and S. Lee, J. Chem. Soc., Perkin Trans. 1 1999, 2661; (d) J. Terao,
H. Watanabe and N. Kambe, J. Am. Chem. Soc. 2005, 127, 3656; (e)
N. Yoshikai, H. Mashima and E. Nakamura, J. Am. Chem. Soc. 2005,
127, 17978; (f) P. Knochel, W. Dohle, N. Gommermann, F. F.
Kneisel, F. Kopp, T. Korn, I. Sapountzis and V. A. Vu, Angew.
Chem., Int. Ed. 2003, 42, 4302; (g) B. H. Lipshutz, J. A. Sclafani and
P. A. Blomgren, Tetrahedron 2000, 56, 2139.
75
Scheme 2. Possible Reaction Pathway
In conclusion, the cyclotrimerization of terminal alkynes can
efficiently catalyzed by direct utilization of
be
80
15 NiCl2ꢁ6H2O/Zn/ZnI2/2ꢀ(benzimidazolyl)ꢀ6ꢀ(1ꢀ(arylimino)ethyl)ꢀ
pyridine system in oneꢀstep in acetonitrile to afford trisubstitutedꢀ
benzene derivatives, the regioꢀselectivity to either 1,2,4ꢀ
trisubstituted or 1,3,5ꢀtrisubstituted benzene derivatives were
relied on the substituents of terminal alkynes and zinc salt.
20 Further investigations of mechanism, additives, and applications
are still in progress.
85
This work was supported by the National Key Basic Research
Program of China (973 program) (2012CB933402) and National
Natural Science Foundation of China (21032004 and 21272132).
13 Examples for carbonꢀheteroatom bond formation, see: (a) B. M.
Rosen, K. W. Quasdorf, D. A. Wilson, N. Zhang, A.ꢀM. Resmerita,
N. K. Garg and V. Percec, Chem. Rev. 2011, 111, 1346; (b) J. P.
Wolfe and S. L. Buchwald, J. Am. Chem. Soc. 1997, 119, 6054; (c)
B. H. Lipshutz and H. Ueda, Angew. Chem., Int. Ed. 2000, 39, 4492;
(d) E. Brenner, R. Schneider and Y. Fort, Tetrahedron 1999, 55,
12829; (f) C. Desmarets, R. Schneider and Y. Fort, Tetrahedron Lett.
2000, 41, 2875; (g) C. Desmarets, R. Schneider and Y. Fort, J. Org.
Chem. 2002, 67, 3029.
14 (a) R. Gao, W.ꢀH. Sun and C. Redshaw, Catal. Sci. Technol.,
2013, 3, 1172; (b) W.ꢀH. Sun, S. Zhang, S. Jie, W. Zhang, Y. Li, H.
Ma, J. Chen, K. Wedeking and R. Fröhlich, J. Organomet. Chem.
2006, 691, 4196; (c) P. Hao, S. Zhang, W.ꢀH. Sun, Q. Shi, S.
Adewuyi, X. Lu and P. Li, Organometallics 2007, 26, 2439; (d) H.
Liu, W. Zhao, X. Hao, C. Redshaw, W. Huang, W.ꢀH. Sun,
Organometallics, 2011, 30, 2418; (e) R. Gao, M. Zhang, T. Liang, F.
Wang and W.ꢀH. Sun, Organometallics 2008, 27, 5641; (f) L. Xiao,
M. Zhang, R. Gao, X. Cao and W.ꢀH. Sun, Aust. J. Chem. 2010, 63,
109.
90
25 Notes and references
95
a
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical
Biology (Ministry of Education), Department of Chemistry, Tsinghua
University, Beijing 100084, China; E-mail: cjxi@tsinghua.edu.cn
b
State Key Laboratory of Elemento-Organic Chemistry, Nankai
30 University, Tianjin 300071, China
100
105
110
† Electronic Supplementary Information (ESI) available: Experimental
procedures, and 1H NMR and 13C NMR data for all compounds. See
DOI: 10.1039/b000000x/
1
W. Reppe and W.J. Schweckendiek, Justus Liebigs Ann. 1948, 560,
35
40
45
104.
2 (a) N. E. Schore, In Comprehensive Organic Synthesis, B. M. Trost, I.
Fleming, L. A. Paquette (Eds.), Pergamon Press: Oxford, 1991; Vol.
5, pp 1129; (b) D. B. Grotjahn, In Comprehensive Organometallic
Chemistry II; E. W. Abel, F. G. A. Stone, G. Wilkinson, L. Hegedus
(Eds.), Pergamon Press: Oxford, 1995; Vol. 12, pp 741; (c) M.
Lautens, W. Klute and W. Tam, Chem. Rev. 1996, 96, 49; (d) S. Saito
and Y. Yamamoto, Chem. Rev. 2000, 100, 2901.
3 (a) K. P. C. Vollhardt, Angew. Chem. Int. Ed. 1984, 23, 539; (b) E.
Negishi, L. S. Harring, Z. Owczarczyk, M. M. Mohamud and M. Ay,
Tetrahedron Lett. 1992, 33, 3253.
15 (a) W.ꢀH. Sun, P. Hao, S. Zhang, Q. Shi, W. Zuo, X. Tang, X. Lu,
Organometallics 2007, 26, 2720; (b) Y. Chen, P. Hao, W. Zuo, K.
Gao and W.ꢀH. Sun, J. Organomet. Chem. 2008, 693 1829.
16 In the cobaltꢀcatalysed cyclotrimerisation of alkynes, the use of a
Lewis acid such as zinc iodide proved to be essential for the catalytic
activity. See: G. Hilt, W. Hess, T. Vogler and C. Hengst, J.
Organomet. Chem. 2005, 690, 5170; reference 9a, and reference 9c.
115 17 (a) SꢀI Ikeda, H. Watanabe and Y. Sato, J. Org. Chem. 1998, 63,
7026; (b) T. Sambaiah, L.ꢀP. Li, D.ꢀJ. Huang, C.ꢀH. Lin, D. K.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3