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S. Saito, Y. Koizumi / Tetrahedron Letters 46 (2005) 4715–4717
4717
CuI
(Cu0)
K.; Kubo, T.; Tokuyama, H.; Fukuyama, T. Synlett 2002,
231–234; (p) Kang, S.-K.; Kim, D.-H.; Park, J.-N. Synlett
2002, 427–430; (q) Ma, D.; Xia, C. Org. Lett. 2001, 3,
2583–2586; (r) Klapars, A.; Antilla, J. C.; Huang, X.;
Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727–7729;
(s) Gujadhur, R.; Venkataraman, D.; Kintigh, J. T.
Tetrahedron Lett. 2001, 42, 4791–4793; (t) Gujadhur, R.
K.; Bates, C. G.; Venkataraman, D. Org. Lett. 2001, 3,
4315–4317; (u) Cacchi, S.; Fabrizi, G.; Goggiamani, A.;
Zappia, G. Org. Lett. 2001, 3, 2539–2541; (v) Wolter, M.;
Klapers, A.; Buchwald, S. L. Org. Lett. 2001, 3, 3803–
3805; (w) Clement, J.-B.; Hayes, J. F.; Sheldrake, H. M.;
Sheldrake, P. W.; Wells, A. S. Synlett 2001, 1423–
1427.
NO2
X
L
R
R
2
L
I or 0
1
Cu
L
L
CuIII or II NO2
III or II
Cu
X
R
R
6. Reviews: (a) Ley, S. V.; Thomas, A. W. Angew. Chem.,
Int. Ed. 2003, 42, 5400–5449; (b) Lindley, J. Tetrahedron
1984, 40(9), 1433–1456.
7. Recent examples: (a) Huang, X.; Anderson, K. W.; Zim,
D.; Jiang, L.; Klapars, A.; Buchwald, S. L. J. Am. Chem.
Soc. 2003, 125, 6653–6655; (b) Strieter, E. R.; Blackmond,
D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125,
13978–13980; (c) Zim, D.; Buchwald, S. L. Org. Lett.
2003, 5, 2413–2415; (d) Hooper, M. W.; Utsunomiya, M.;
Hartwig, J. F. J. Org. Chem. 2003, 68, 2861–2873; (e)
Kuwano, R.; Utsunomiya, M.; Hartwig, J. F. J. Org.
Chem. 2002, 67, 6479–6486; (f) Alcazar-Roman, L. M.;
Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 12905–12906;
(g) Stauffer, S. R.; Lee, S.; Stambuil, J. P.; Hauck, S. I.;
Hartwig, J. F. Org. Lett. 2000, 2, 1423–1426; (h) Alcazar-
Roman, L. M.; Hartwig, J. F.; Rheingold, A. L.; Liable-
Sands, L. M.; Guzei, I. A. J. Am. Chem. Soc. 2000, 122,
4618–4630.
-
X-
NO2
(KNO2 - 18-crown-6
or n-Bu4NNO2)
Scheme 1.
References and notes
1. (a) Nitration; Albright, L. F., Carr, R. V. C., Schmitt, R.
J., Eds. ACS Symposium Series 623; American Chemical
Society: Washington, DC, 1996; (b) Olah, G. A.; Malho-
tra, R.; Narang, S. C. Nitration: Methods and Mechanisms;
VCH: New York, 1989.
2. (a) Kyodai-nitration: Nonoyama, N.; Mori, T.; Suzuki, H.
Russ. J. Org. Chem. 1998, 34, 1521–1531; (b) Ridd, J. H.
Acta Chem. Scand. 1998, 52, 11–22; (c) Mori, T.; Suzuki,
H. Synlett 1995, 383–392; (d) Suzuki, H.; Murashima, T.;
Shimizu, K.; Tsukamoto, K. Chem. Lett. 1991, 817–818.
3. Nitration of phenylmetals: Tani, K.; Lukin, K.; Eaton,
P. E. J. Am. Chem. Soc. 1997, 119, 1476–1477.
4. ipso-Nitration of arylboronic acids: (a) Prakash, G. K. S.;
Panja, C.; Mathew, T.; Surampudi, V.; Petasis, N. A.;
Olah, G. A. Org. Lett. 2004, 6, 2205–2207; (b) Thiebes, C.;
Prakash, G. K. S.; Petasis, N. A.; Olah, G. A. Synlett
2000, 1485–1487.
5. Recent examples: (a) Klapars, A.; Parris, S.; Anderson, K.
W.; Buchwald, S. L. J. Am. Chem. Soc. 2004, 126, 3529–
3533; (b) Jiang, L.; Job, G. E.; Klapars, A.; Buchwald, S.
L. Org. Lett. 2003, 5, 3667–3669; (c) Padwa, A.; Crawford,
K. R.; Rashatasakhon, P.; Rose, M. J. Org. Chem. 2003,
68, 2609–2617; (d) Lu, Z.; Twieg, R. J.; Huang, S. D.
Tetrahedron Lett. 2003, 44, 6289–6292; (e) Kwong, F. Y.;
Buchwald, S. L. Org. Lett. 2003, 5, 793–796; (f) Malle-
sham, B.; Rajesh, B. M.; Reddy, P. R.; Srinivas, D.;
Trehan, S. Org. Lett. 2003, 5, 963–965; (g) Evindar, G.;
Batey, R. A. Org. Lett. 2003, 5, 133–136; (h) Enguehard,
C.; Allouchi, H.; Gueiffier, A.; Buchwald, S. J. Org. Chem.
2003, 68, 4367–4370; (i) Ma, D.; Xia, C.; Jiang, J.; Zhang,
J.; Tang, W. J. Org. Chem. 2003, 68, 442–451; (j) Kwong,
F. Y.; Klapars, A.; Buchwald, S. L. Org. Lett. 2002, 4,
581–584; (k) Klapars, A.; Huang, X.; Buchwald, S. L. J.
Am. Chem. Soc. 2002, 124, 7421–7428; (l) Job, G. E.;
Buchwald, S. L. Org. Lett. 2002, 4, 3703–3706; (m)
Crawford, K. R.; Padwa, A. Tetrahedron Lett. 2002, 43,
7365–7368; (n) Kelkar, A. A.; Patil, N. M.; Chaudhari, R.
V. Tetrahedron Lett. 2002, 43, 7143–7146; (o) Yamada,
8. (a) Reviews: Hartwig, J. F. Pure Appl. Chem. 1999, 71,
1417–1423; (b) Hartwig, J. F. Acc. Chem. Res. 1998, 31,
852–860; (c) Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.;
Buchwald, S. L. Acc. Chem. Res. 1998, 31, 805–818; (d)
Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046–
2067; (e) Hartwig, J. F. Synlett 1997, 329–341.
9. To the best of our knowledge, only one example of a
CuNO2-mediated nitration of an aromatic compound
(bromoazulene) has been reported in the literature. See:
Nefedov, V. A.; Tarygina, L. K. J. Org. Chem., USSR
1976, 12, 1730–1734.
10. (a) Zanon, J.; Klapars, A.; Buchwald, S. L. J. Am. Chem.
Soc. 2003, 125, 2890–2891; (b) Buchwald, S. L.; Klapars,
A. J. Am. Chem. Soc. 2002, 124, 14844–14845.
11. Representative procedure: Cu bronze was purchased from
Aldrich (Cu powder, 1–5 lm, cat. No. 292583), and used
as received. A tube with screw-cap was charged with 1a
(234 mg, 1.0 mmol), Cu bronze (3.2 mg, 0.05 mmol), tetra-
n-butylammonium nitrite (346.2 mg, 1.2 mmol), anhy-
drous DMF (0.3mL) and N,N0-dimethylethylenediamine
(10.6 lL, 0.10 mmol) under Ar. The mixture was stirred at
100 °C for 3h. The reaction mixture was directly purified
by silica gel column chromatography (hexane/
AcOEt = 30:1) to give 2a as a pale yellow oil (124 mg,
0.81 mmol, 81%).
12. (a) Xi, M.; Bent, B. E. J. Am. Chem. Soc. 1993, 115, 7426–
7433; (b) Paine, A. J. J. Am. Chem. Soc. 1987, 109, 1496–
1502; (c) Cohen, T.; Cristea, I. J. Am. Chem. Soc. 1976, 98,
748–753; (d) Cohen, T.; Lewin, A. H. Tetrahedron Lett.
1965, 50, 4531–4536.
13. The Cu(I) species could be generated from Cu bronze and
haloarenes. See, Ref. 12d. Alternatively, the Cu(0) species
might act as the catalyst for this reaction.