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Table 1 5-Cuprated imidazole derivatives and their reaction with
electrophiles
Entry Copper reagent 3 Electrophile Product of type 4 Yielda (%)
1
2
3
4
90
86
81
74
3a
3a
3a
EtCOCl
c-PentCOCl
ClCOCO2Et
Scheme 2
Notes and references
1 (a) T. L. Gilchrist, Heterocyclic Chemistry, Longman, Harlow, UK,
1997; (b) J. A. Joule and K. Mills, Heterocyclic Chemistry, Blackwell
Science, Oxford, 2000.
2 (a) D. E. N. Jacquot, M. Zo¨llinger and T. Lindel, Angew. Chem., Int.
Ed., 2005, 44, 2295; (b) H. Hoffmann and T. Lindel, Synthesis, 2003,
1753; (c) J. Zhong, Z. Li and R. Huang, Nat. Prod. Rep., 2002, 19, 454;
(d) D. D. Baker and K. A. Alvi, Curr. Opin. Biotechnol., 2004, 15, 576;
(e) M. M. Bastos, A. C. Barbosa, A. C. Pinto, W. B. Kover, Y. Taheuchi
and N. Boechat, J. Braz. Chem. Soc., 2001, 12, 417.
3 (a) B. H. Lipshutz and S. Sengupta, Org. React., 1992, 41, 135; (b)
B. H. Lipshutz, B. Huff and W. Hagen, Tetrahedron Lett., 1988, 29,
3411; (c) B. H. Lipshutz, P. Fatheree, W. Hagen and K. L. Stevens,
Tetrahedron Lett., 1992, 33, 1041; (d) B. L. Eriksen, P. Vedso and
M. Begtrup, J. Org. Chem., 2001, 66, 8344; (e) M. R. Grimmett, Adv.
Heterocycl. Chem., 1980, 27, 241.
5
6
7
93
84
85
3b
3b
EtCOCl
PhCOCl
4 Y. Chen, H. V. R. Dias and C. J. Lovely, Tetrahedron Lett., 2003, 44,
1379.
5 For previous preparation of functionalized copper reagents, see: (a)
E. J. Corey and G. H. Posner, J. Am. Chem. Soc., 1968, 90, 5615; (b)
Y. Kondo, T. Matsudaira, J. Sato, N. Muraka and T. Sakamoto,
Angew. Chem., 1996, 108, 818; Y. Kondo, T. Matsudaira, J. Sato,
N. Muraka and T. Sakamoto, Angew. Chem., Int. Ed. Engl., 1996, 35,
736; (c) G. W. Ebert and R. D. Rieke, J. Org. Chem., 1984, 49, 5281; (d)
R. D. Rieke, R. H. Wehmeyer, T. C. Wu and G. W. Ebert, Tetrahedron,
1989, 45, 443; (e) G. W. Ebert, J. W. Cheasty, S. S. Tehrani and
E. Aouad, Organometallics, 1992, 11, 1560; (f) G. W. Ebert,
D. R. Pfennig, S. D. Suchan and T. A. Donovan, Tetrahedron Lett.,
1993, 34, 2279.
6 (a) C. Piazza and P. Knochel, Angew. Chem., Int. Ed., 2002, 41, 3263; (b)
X. Yang, T. Rotter, C. Piazza and P. Knochel, Org. Lett., 2003, 5, 1229;
(c) X. Yang and P. Knochel, Synlett, 2004, 81; (d) X. Yang,
A. Althammer and P. Knochel, Org. Lett., 2004, 6, 1665.
8
9
3b
3b
3b
2-FurCOCl
ClCOCO2Et
81
76
54
7 For the preparation of diorganozincs bearing an aldehyde function:
F. F. Kneisel, H. Leuser and P. Knochel, Synthesis, 2005, 2625.
8 For the preparation of functionalized organometallic reagents, see: (a)
P. Knochel, Handbook of Functionalized Organometallics, Wiley-VCH,
Weinheim, 2005; (b) N. Krause, Modern Organocopper Chemistry,
Wiley-VCH, Weinheim, 2002; (c) M. d’Augustin, L. Palais and
A. Alexakis, Angew. Chem., Int. Ed., 2005, 44, 1376; (d) R. Naasz,
L. A. Arnold, M. Pineschi, E. Keller and B. L. Feringa, J. Am. Chem.
Soc., 1999, 121, 1104; (e) I. Marek and J.-F. Normant, Chem. Rev.,
1996, 96, 3241; (f) R. F. W. Jackson, I. Rilatt and P. J. Murray, Chem.
Commun., 2003, 1242.
10
9 NMP often accelerates many organometallic transformations; see also:
(a) F. F. Kneisel, M. Dochnahl and P. Knochel, Angew. Chem., Int. Ed.,
2004, 43, 1017; (b) F. F. Kneisel and P. Knochel, Synlett, 2002, 1799.
10 For the influence of the electron-density of aromatic ring on the iodine–
metal exchange reaction, see: (a) I. Sapountzis and P. Knochel, Angew.
Chem., Int. Ed., 2004, 43, 897; (b) P. Knochel, W. Dohle,
N. Gommermann, F. F. Kneisel, F. Kopp, T. Korn, I. Sapountzis
a
Isolated yields of analytically pure products.
This journal is ß The Royal Society of Chemistry 2006
Chem. Commun., 2006, 2170–2172 | 2171