PAPER
Cu Nanoparticle Catalyzed Preparation of Aryl Malonates
1481
Diethyl 2-(2-Chlorophenyl)malonate (2k)19
Purified by column chromatography on silica gel using EtOAc in
hexane (10%) as eluent; yield: 202 mg (89%); colorless oil.
Anal. Calcd for C H O : C, 56.69; H, 5.55. Found: C, 56.75; H,
5.51.
12
14
6
1
H NMR (400 MHz, CDCl ): δ = 7.47 (t, J = 2.8 Hz, 1 H), 7.40–7.38
3
Acknowledgment
(
(
1
m, 1 H), 7.28–7.25 (m, 2 H), 5.20 (s, 1 H), 4.27–4.18 (m, 4 H), 1.28
t, J = 7.2 Hz, 6 H).
The authors wish to record the help provided by the NMR facility
installed in the Department of Chemistry, University of Kalyani,
Kalyani, India under the DST-FIST scheme. Helpful discussion
with Dr. K. Ghosh of the same department is gratefully acknow-
ledged. Help with laboratory facilities from Prof. T. Basu, Depart-
ment of Biochemistry & Biophysics of the same university is
acknowledged. The Editor and reviewers are thanked for improving
the quality of the manuscript. Help from DST-PURSE grant is
acknowledged.
3
C NMR (125 MHz, CDCl ): δ = 167.7, 134.4, 131.2, 130.2, 129.5,
3
1
29.4, 127.1, 62.0, 54.6, 14.0.
LC-MS: m/z = 270.7 (M + H).
Anal. Calcd for C H ClO : C, 57.68; H, 5.59. Found: C, 57.59; H,
1
3
15
4
5
.62.
Diethyl 2-(2-Pyridyl)malonate (5a)12
Purified by column chromatography on silica gel using EtOAc in
hexane (24%) as eluent; yield: 175 mg (76%); brown oil.
1
H NMR (400 MHz, CDCl ): δ = 8.56 (d, J = 4.0 Hz, 1 H), 7.72–
.69 (m, 1 H), 7.49 (d, J = 7.6 Hz, 1 H), 7.25 (d, J = 8.4 Hz, 1 H),
.92 (s, 1 H), 4.29–4.15 (m, 4 H), 1.28 (t, J = 7.2 Hz, 6 H).
Supporting Information for this article is available online at
3
7
4
http://www.thieme-connect.com/ejournals/toc/synthesis. Included
1
13
are spectra for all compounds including H NMR, C NMR,
LCMS, EI-MS, and the table containing undesirable conditions for
Cu NP-catalyzed coupling of 1-iodo-4-methoxybenzene with di-
13
C NMR (125 MHz, CDCl ): δ = 167.5, 153.1, 149.4, 147.2, 136.8,
3
1
24.1, 123.7, 123.0, 62.6, 62.0, 60.6, 14.0, 13.9.
ethyl malonate.SnoIuiofpg
r
t
iornat
S
nugIopinfr t
m
rat
LC-MS: m/z = 237.5 (M + H).
Anal. Calcd for C H NO : C, 60.75; H, 6.37; N, 5.90. Found: C,
1
2
15
4
References
60.79; H, 6.34; N, 5.86.
(
1) For selected examples, see the following: Vancomycin:
a) Sheldrick, G. M.; Jones, P. G.; Kennard, O.; Williams, D.
H.; Smith, G. A. Nature 1978, 271, 223. Lucuminic acid:
b) Takeda, T.; Gonda, R.; Hatano, K. Chem. Pharm. Bull.
997, 45, 697. Polymastiamide A: (c) Kong, F.; Andersen,
Diethyl 2-(3-Methoxy-6-methylpyridin-2-yl)malonate (5b)
Purified by column chromatography on silica gel using EtOAc in
hexane (25%) as eluent; yield: 177 mg (79%); light yellow oil.
(
(
1
IR (neat): 826, 1036, 1150, 1254, 1308, 1470, 1743, 2983, 3467
–
1
cm .
R. J. J. Org. Chem. 1993, 58, 6924. Chloropeptin I and II:
(d) Hegde, V. R.; Dai, P.; Patel, M.; Gullo, V. P.
Tetrahedron Lett. 1998, 39, 5683. Vulculic acid: (e) Kimura,
Y.; Nishibe, M.; Nakajima, H.; Hamasaki, T. Agric. Biol.
Chem. 1991, 55, 1137.
1
H NMR (500 MHz, CDCl ): δ = 7.08 (m, 2 H), 5.01 (s, 1 H), 4.28–
3
4.24 (m, 4 H), 3.78 (s, 3 H), 2.44 (s, 3 H), 1.29 (t, J = 7.0 Hz, 6 H).
13
C NMR (125 MHz, CDCl ): δ = 167.8, 151.5, 149.4, 142.8, 123.1,
3
118.3, 61.5, 56.2, 55.6, 23.3, 14.1.
(
2) Beyer, J.; Jensen, B. S.; Strøbæk, D.; Christophersen, P.;
Teuber, L. WO Patent 00/37422, 2000.
MS (EI) m/z = 281.1 (M+).
Anal. Calcd for C H NO : C, 59.78; H, 6.81; N, 4.98. Found: C,
(3) Rieu, J.-P.; Boucherle, A.; Cousse, H.; Mouzin, G.
1
4
19
5
59.81; H, 6.83; N, 4.97.
Tetrahedron 1986, 42, 4095.
(
(
4) For a review, see: Culkin, D. A.; Hartwig, J. F. Acc. Chem.
Res. 2003, 36, 234.
Diethyl 2-(6-Methoxypyridin-3-yl)malonate (5c)18
Purified by column chromatography on silica gel using EtOAc in
hexane (38%) as eluent; yield: 163 mg (72%); orange oil.
5) (a) Ullmann, F. Ber. Dtsch. Chem. Ges. 1903, 36, 2382. For
reviews, see: (b) Lindley, J. Tetrahedron 1984, 40, 1433.
(c) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire,
M. Chem. Rev. 2002, 102, 1359. (d) Ley, S. V.; Thomas, A.
W. Angew. Chem. Int. Ed. 2003, 42, 5400. (e) Kunz, K.;
Scholz, U.; Ganzer, D. Synlett 2003, 2428. (f) Beletskaya, I.
P.; Cheprakov, A. V. Coord. Chem. Rev. 2004, 248, 2337.
(g) Sperotto, E.; van Klink, G. P. M.; van Koten, G.; de
Vries, J. G. Dalton Trans. 2010, 39, 10338.
1
H NMR (500 MHz, CDCl ): δ = 7.42 (d, J = 9.5 Hz, 1 H), 7.37 (s,
3
1
1
H), 6.58 (d, J = 9.5 Hz, 1 H), 4.29 (s, 1 H), 4.24–4.21 (m, 4 H),
.29 (t, J = 7.0 Hz, 6 H).
13
C NMR (125 MHz, CDCl ): δ = 173.1, 167.6, 162.7, 142.0, 140.9,
3
1
3
38.5, 137.6, 120.4, 120.3, 120.2, 111.6, 62.3, 53.9, 38.0, 37.9,
6.8, 14.0.
MS (EI): m/z = 267.1 (M+).
(
6) (a) Ma, D.; Zhang, Y.; Yao, J.; Wu, S.; Tao, F.. J. Am. Chem.
Soc. 1998, 120, 12459. (b) Ma, D.; Xia, C. Org. Lett. 2001,
Anal. Calcd for C H NO : C, 58.42; H, 6.41; N, 5.24. Found: C,
1
3
17
5
58.37; H, 6.44; N, 5.25.
3
, 2583. (c) Klapars, A.; Antilla, J. C.; Huang, X.;
Buchwald, S. L. J. Am. Chem. Soc. 2001, 123, 7727.
d) Gujadhur, R. K.; Bates, C. G.; Venkataraman, D. Org.
Diethyl 2-(5-Formylfuran-2-yl)malonate (5d)
Purified by column chromatography on silica gel using EtOAc in
hexane (30%) as eluent; yield: 183 mg (80%); brown oil.
(
Lett. 2001, 3, 4315. (e) Antilla, J. C.; Klapars, A.; Buchwald,
S. L. J. Am. Chem. Soc. 2002, 124, 11684. (f) Kwong, F. Y.;
Klapars, A.; Buchwald, S. L. Org. Lett. 2002, 4, 581.
IR (neat): 1027, 1221, 1372, 1396, 1517, 1679, 1740, 2985, 3124,
–
1
3
478 cm .
(g) Kwong, F. Y.; Buchwald, S. L. Org. Lett. 2003, 5, 793.
1
(h) Shen, R.; Lin, C. T.; Bowman, E. J.; Bowman, B. J.;
H NMR (400 MHz, CDCl ): δ = 9.61 (s, 1 H), 7.23 (d, J = 3.2 Hz,
3
1
H), 6.70 (d, J = 3.6 Hz, 1 H), 4.85 (s, 1 H), 4.28–4.19 (m, 4 H),
Porco, J. A. Jr. J. Am. Chem. Soc. 2003, 125, 7889.
(i) Cristau, H. J.; Cellier, P. P.; Spindler, J. F.; Taillefer, M.
Chem. Eur. J. 2004, 10, 5607. (j) Ma, D.; Cai, Q. Synlett
1.30 (t, J = 7.2 Hz, 6 H).
13
C NMR (125 MHz, CDCl ): δ = 177.7, 165.2, 152.4, 112.3, 111.4,
3
2
1
004, 128. (k) Pan, X.; Cai, Q.; Ma, D. Org. Lett. 2004, 6,
809. (l) Zhu, W.; Ma, D. Chem. Commun. 2004, 888.
62.7, 52.4, 34.3, 14.1, 13.9.
LC-MS: m/z = 254.5 (M + H).
(
m) Deng, W.; Wang, Y.; Zou, W.; Liu, L.; Guo, Q.
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Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 1475–1482