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ChemComm
DOI: 10.1039/C3CC46419A
complexes.21,22 Thus it seems that the role of the alkyne additive
is to stabilize reactive alkylcopper intermediates, as Kambe et al.
suggested.9
Stang), WileyꢀVCH, Weinheim, Germany, 1998, pp. 1–47; (e) E.
Negishi, Acc. Chem. Res. 1982, 15, 340; (f) E. Erdik, Tetrahedron
1992, 48, 9577; (g) Y. Nakao and T. Hiyama, Chem. Soc. Rev. 2011,
40, 4893; (h) A. Devasagayaraj, T. Studemann, P. Knochel, Angew.
Chem., Int. Ed. 1995, 34, 2723.
In order to gain some insight into the reaction mechanism, 6ꢀ
bromoꢀ1ꢀhexene and (bromomethyl)cyclopropane and were
reacted with nꢀBuMgCl. In the reaction of 6ꢀbromoꢀ1ꢀhexene
with nꢀBuMgCl (Eq. 1), 1ꢀdecene was formed, but no cyclized
product was observed. However, in the case of
(bromomethyl)cyclopropane (Eq. 2), pentylcyclopropane and 1ꢀ
10 octene were obtained in a ratio of 12.5:1 with a total 55 % yield.
These observations indicate that the coupling reaction occur
mainly via an SN2 mechanism.9,11 In addition, the Cu NPꢀ
catalyzed crossꢀcouplings undergo a minor radical pathway. It
has been reported23 that the rearrangement products were
15 observed in the reaction of activated haloalkanes with alkenes in
the presence of copper metal.
60
5
2. (a) K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94,
4374; (b) Tamao, K.; Kiso, Y.; Sumitani, K.; Kumada, M. J. Am.
Chem. Soc. 1972, 94, 9268ꢀ9269
3. R. J. P. Corriu, J. P. Masse, J. Chem. Soc., Chem. Commun. 1972, 144.
65 4. Pd: (a) J. Terao, Y. Naitoh, H. Kuniyasu, N. Kambe, Chem. Lett. 2003,
32, 890; Ag: (b) H. Someya, H. Ohmiya, H. Yorimitsu, K. Oshima,
Org. Lett. 2008, 10, 969; (c) H. Someya, H. Yorimitsu, K. Oshima,
Tetrahedron Lett. 2009, 50, 3270. Fe: (d) K. G. Dongol, H. Koh, M.
Sau, C. L. L. Chai, Adv. Synth. Catal. 2007, 349, 1015; (e) M. G.
Cenios, F. Tato, E. Bunuel, P. Calle, D. J. Cárdenas, Chem. Sci. 2013,
4. 1098. Ni: (f) P. Ren, O. Vechokin, K. von Allmen, R. Scopelliti,
X. Hu, J. Am. Chem. Soc. 2011, 133, 7084; Co: (g) T. Tsuji, H.
Yorimitsu, K. Oshima, Angew. Chem. Int. Ed. 2002, 41, 4137; (h) S.
P. Singh, J. Terao, N. Kambe, Tetrahedron Lett. 2009, 50, 5644. Cu:
(i) R. Shimizu, E. Yoneda, T. Fuchikami, Tetrahedron Lett. 1996, 37,
5557; (j) G. Cahiez, O. Gager, J. Buendia, Synlett 2010, 299; (k) M.ꢀ
B. Li, X.ꢀL. Tang, S.ꢀK. Tian, Adv. Synth. Catal. 2011, 353, 1980.
5. Tamura, M.; Kochi, J. K. J. Organomet. Chem. 1972, 42, 205.
6. G. Cahiez, C. Chaboche, M. Jézéquel, Tetrahedron 2000, 56, 2733.
70
75
(1)
80 7. (a) J. Terao, H. Watanabe, A. Ikumi, H. Kuniyasu, N. Kambe, J. Am.
Chem. Soc. 2002, 124, 4222; (b) J. Terao, A. Oda, A. Ikumi, A.
Nakamura, H. Kuniyasu, N. Kambe, Angew. Chem. Int. Ed. 2003, 42,
3412; (c) J. Terao, H. Todo, H. Watanabe, A. Ikumi, N. Kambe,
Angew. Chem. Int. Ed. 2004, 43, 6180.
85 8. J. Terao, A. Ikumi, H. Kuniyasu, N. Kambe, J. Am. Chem. Soc. 2003,
125, 5646.
9. J. Terao, H. Todo, S. A. Begum, H. Kuniyasu, N. Kambe, Angew.
Chem., Int. Ed. 2007, 46, 2086.
20
20 (2)
Although the exact mechanism for the reduction is not clear, we
think that it is similar to that of other homogeneous copperꢀ
catalyzed reactions (see the SI).9,24
In conclusion, we have developed a Cu NPꢀbased crossꢀcoupling
10. G. Cahiez, C. Chaboche, A. Gilliani, C. Duplais, A. Moyeux, Adv.
25 method that is remarkably simple and general. The Cu NPs used
in this study are commercially available and the catalytic system
doesn’t need any pretreatment or preformed supports and ligands.
The catalytic system is quite effective for the crossꢀcoupling of
primary alkyl bromides or chlorides with alkyl or aryl Grignard
30 reagents. In view of the broad scope of the substrates, functional
group tolerance, high reaction efficiencies, high product yields,
and reusability, the Cu NPꢀcatalyzed crossꢀcoupling reaction can
be expected to find wide synthetic applications. We are currently
exploring the use of other additives for the Cu NPꢀcatalysis to
35 further widen the reaction scope of the crossꢀcouplings and to
expand the use of Cu NPs as catalysts in other related crossꢀ
coupling reactions. We are also studying what the active species
is in the Cu NPsꢀcatalyzed crossꢀcoupling reaction.
90
95
Synth. Catal. 2008, 350, 1484.
11. P. Ren, L.ꢀA. Stem, X. Hu, Angew. Chem., Int. Ed. 2012, 51, 9110.
12. C.ꢀT. Yang, Z.ꢀQ. Zhang, J. Liang, J.ꢀH. Liu, X.ꢀY. Lu, H.ꢀH. Chen,
L. Liu, J. Am. Chem. Soc. 2012, 134, 11124.
13. T. Iwasaki, H. Takagawa, S. P. Singh, H. Kuniyasu, N. Kambe, J. Am.
Chem. Soc. 2013, 135, 9604.
14. J.ꢀF. Soulé, H. Miyamura, S. Kobayashi, J. Am. Chem. Soc. 2013, 135,
10602.
15. J. H. Park, Y. K. Chung, Dalton Trans. 2008, 2369.
16. O. Vechorkin, V. Proust, X. Hu, J. Am. Chem. Soc. 2009, 131, 9756.
100 17. (a) Burns, D. H.; Miller, J. D.; Chan, H. K.; Delaney, M. O. J. Am.
Chem. Soc. 1997, 119, 2125; (b) G. Cahiez, O. Gager, J. Buendia, J.
Synlett 2010, 299; (c) I. P. Beletskaya, A. V. Cheprakov, Coord.
Chem. Rev. 2004, 248, 2337.
18. According to the TEM image and XRD data of the purchasing copper
105
nanoparticles, the lattices of Cu nanoparticles were observed with
those of Cu2O nanoparticles (with the ratio of 3:1 Cu and Cu2O). See
the Supporting Information for details.
This work was supported by the National Research Foundation of
40 Korea (NRF) (2007ꢀ0093864) and the Basic Science Research
Program through the NRF funded by the Ministry of Education,
Science and Technology (R11ꢀ2005ꢀ065). JHK thank the Brain
Korea 21 fellowships.
19
.
For comparison, the same amount of Cu present in a soluble catalyst
CuCl2 under our reaction conditions gave a trace amount of product.
110 20. J. Terao, N. Kambe, Acc. Chem. Res. 2008, 41, 1545.
21. M. A. Blitz, S. A. Mitchell, P. A. Hackett, J. Phys. Chem. 1993, 97,
5298.
22. J. A. Howard, R. Sutcliffe, J. S. Tse, B. Mile, Organometallics 1984,
3, 859.
Notes and references
115 23. (a) J. O. Metzger, R. Mahler, Angew. Chem., Int. Ed. 1995, 34, 902.
For Cu NPꢀcatalyzed reaction via an electron transfer reaction, see:
(b) B. C. Ranu, A. Saha, R. Jana, Adv. Synth. Catal. 2007, 349, 2690.
24. G. Cahiez, O. Gager, J. Buendia, Angew. Chem. Int. Ed. 2010, 49,
1278 .
45 Intelligent Textile System Research Center, and Department of Chemistry,
College of Natural Sciences Institution, Seoul National University, Seoul,
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
50 DOI: 10.1039/b000000x/
1. (a) A. Suzuki, Pure Appl. Chem. 1985, 57, 1749; (b) R. F. Heck, Org.
React. 1982, 27, 345; (c) D. Milstein and J. K. Stille, J. Am. Chem.
Soc. 1979, 101, 4981; (d) E. I. Negishi and F. Liu, in Metal-
55
Catalyzed Cross-Coupling Reactions, (Eds: F. Diederich and P. J.
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