2
906
B. Kaboudin, M. Khodamorady
LETTER
Table 1 N-Formylation of Amines with Triethyl Orthoformate in
Hachiya, I. Chem. Lett. 1996, 407.
Water at Reflux or Microwave Irradiation
(9) (a) Green, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis, 3rd ed.; Wiley-Interscience: New York,
O
H2O
R
1
1
999. (b) Sheehan, J. C.; Yang, D. D. H. J. Am. Chem. Soc.
958, 80, 1154. (c) Strazzolini, P.; Giumanini, A. G.; Cauci,
RNH2
+
HC(OEt)3
N
H
H
S. Tetrahedron 1990, 46, 1081. (d) Blicke, F. F.; Lu, C.-J.
J. Am. Chem. Soc. 1952, 74, 3933. (e) Waki, J.;
1
2
Methoda
Yields of 2 (%)b
Meienhofer, J. J. Org. Chem. 1977, 42, 2019. (f) Chen, F.
M. F.; Benoiton, N. L. Synthesis 1979, 709. (g) Yale, H. L.
J. Org. Chem. 1971, 36, 3238. (h) Kisfaludy, L.; Laszlo, O.
Synthesis 1987, 510. (i) Neveux, M.; Bruneaum, C.;
Entry R of 1
Time (h)
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
Ph
–c
A
B
B
B
A
B
A
B
A
A
A
A
A
A
B
24
24
2
35
85
87
50
78
53
83
60
80
51
63
62
43
41
42
–d
Ph
Dixneuf, P. H. J. Chem. Soc., Perkin Trans. 1 1991, 1197.
10) Duezek, W.; Deutsch, J.; Vieth, S.; Nicolas, H.-J. Synthesis
(
(
Ph
1
996, 37.
11) Mihara, M.; Ishino, Y.; Minakata, S.; Komatsu, M. Synthesis
003, 2317.
(12) Reddy, P. G.; Kumar, G. D. K.; Baskaran, S. Tetrahedron
000, 41, 9149.
BnCH2
Bn
3
2
2
2
2-EtC H4
24
3
(13) Luca, L. D.; Giacomelli, G.; Porcheddu, A.; Salaris, M.
6
Synlett 2004, 2570.
3-O NC H
4
2
6
(
14) Desai, B.; Danks, T. N.; Wagner, G. Tetrahedron Lett. 2005,
6, 955.
15) (a) Hosseini-Sarvari, M.; Sharghi, J. J. Org. Chem. 2006, 71,
4
3-MeOC H4
48
3
6
(
6652. (b) Khazaei, A.; Mehdipour, E. Iran Polym. J. 1999, 8,
4-MeOC H4
6
257. (c) Bao, K.; Zhang, W.; Bu, X.; Song, Z.; Zhang, L.;
1
1
1
1
1
1
1
4-ClC H4
24
24
24
24
24
36
2
Cheng, M. Chem. Commun. 2008, 5428. (d) Tumma, H.;
Nagaraju, N.; Reddy, K. V. J. Mol. Catal. A: Chem. 2009,
310, 121. (e) Brahmachari, G.; Laskar, S. Tetrahedron Lett.
6
6
4-BrC H4
2010, 51, 2319.
3-Cl-2-MeC H
6
3
(
(
16) Ishida, T.; Haruta, M. Chem. Commun. 2009, 538.
17) (a) Chancellor, T.; Morton, C. Synthesis 1994, 1023.
3-Cl-4-FC H3
6
(
b) Roberts, R.; Vogt, P. J. Am. Chem. Soc. 1956, 78, 4778.
(c) Swaringen, R.; Eaddy, J.; Henderson, T. J. Org. Chem.
980, 45, 3986.
4-NCC H4
6
1
1-naphthyl
3-pyridyl
(
(
18) (a) Grieco, P. A. Organic Synthesis in Water; Blackie
Academic and Professional: London, 1998. (b) Demko,
Z. P.; Sharpless, K. B. J. Org. Chem. 2001, 66, 7945.
(c) Li, C.-J. Chem. Rev. 2005, 105, 3095. (d) Azizi, N.;
Aryanasab, F.; Torkiyan, L.; Ziyaei, A.; Saidi, M. R. J. Org.
Chem. 2006, 71, 3634. (e) Kaboudin, B.; Sorbiun, M.
Tetrahedron Lett. 2007, 48, 9015.
a
b
c
d
Method A: reflux in water. Method B: microwave-assisted at 90 °C.
Yields refer to the isolated pure products.
Reaction at ambient temperature.
Mixture of unknown products.
19) (a) Balakrishna, M. S.; Kaboudin, B. Tetrahedron Lett.
2
001, 42, 1127. (b) Kaboudin, B.; Navaee, K. Heterocycles
2001, 55, 1443. (c) Kaboudin, B.; Navaee, K. Heterocycles
003, 60, 2287. (d) Kaboudin, B.; Saadati, F. J. Heterocycl.
Acknowledgment
2
The authors gratefully acknowledge support by the Institute for Ad-
vanced Studies in Basic Sciences (IASBS) Research Council under
grant No. G2009IASBS120.
Chem. 2005, 42, 699. (e) Kaboudin, B.; Saadati, F.
Heterocycles 2005, 65, 353. (f) Kaboudin, B.; Rahmani, A.
Synthesis 2003, 2705. (g) Kaboudin, B.; Saadati, F.
Synthesis 2004, 1249. (h) Kaboudin, B.; Rahmani, A. Org.
Prep. Proced. Int. 2004, 36, 82. (i) Kaboudin, B.; Moradi,
K. Tetrahedron Lett. 2005, 46, 2989. (j) Kaboudin, B.;
Haghighat, H. Tetrahedron Lett. 2005, 46, 7955.
(k) Kaboudin, B.; Haghighat, H.; Yokomatsu, T. J. Org.
Chem. 2006, 71, 6604. (l) Kaboudin, B.; Karimi, M. Bioorg.
Med. Chem. Lett. 2006, 16, 5324. (m) Kaboudin, B.;
Farjadian, F. Beilstein J. Org. Chem. 2006, 2, 4.
References and Notes
(
1) Jackson, A.; Meth-Cohn, O. J. Chem. Soc., Chem. Commun.
995, 1319.
1
(
2) Chen, B.-C.; Bednarz, M. S.; Zhao, R.; Sundeen, J. E.; Chen,
P.; Shen, Z.; Skoumbourdis, A. P.; Barrish, J. C.
Tetrahedron Lett. 2000, 41, 5453.
(
3) (a) Kobayashi, K.; Nagato, S.; Kawakita, M.; Morikawa, O.;
Konishi, H. Chem. Lett. 1995, 575. (b) Kakehi, A.; Ito, S.;
Hayashi, S.; Fujii, T. Bull. Chem. Soc. Jpn. 1995, 68, 3573.
4) Han, Y.; Cai, L. Tetrahedron Lett. 1997, 38, 5423.
5) Mahmoud, K. F.; Newtown, S. P. US 5,155,267, 1992.
6) Dieter, A.; Gerhard, K. US 4,419,297, 1983.
(n) Yamagishi, T.; Kusano, T.; Kaboudin, B.; Yokomatsu,
T.; Sakuma, C.; Shibuya, S. Tetrahedron 2003, 59, 767.
(o) Kaboudin, B.; Haruki, T.; Yamaghishi, T.; Yokomatsu,
T. Tetrahedron 2007, 63, 8199. (p) Kaboudin, B.; Haruki,
T.; Yamagishi, T.; Yokomatsu, T. Synthesis 2007, 3226.
(q) Kaboudin, B.; Haghighat, H.; Yokomatsu, T.
(
(
(
(
7) Downie, I. M.; Earle, M. J.; Heaney, H.; Shuhaibar, K. F.
Tetrahedron: Asymmetry 2008, 19, 862. (r) Kaboudin, B.;
Saadati, F. Tetrahedron Lett. 2009, 50, 1450.
Tetrahedron 1993, 49, 4015.
(
8) (a) Kobayashi, S.; Nishio, K. J. Org. Chem. 1994, 59, 6620.
(20) The amine (3 mmol) and triethyl orthoformate (12 mmol)
was added to H O (8 mL), and the solution was stirred for 3–
48 h at reflux or 2–3 h under microwave irradiation at 90 °C
(b) Clayden, J. Organic Chemistry; Oxford University Press:
2
Oxford, 2001, 276–296. (c) Kobayashi, S.; Yasuda, M.;
Synlett 2010, No. 19, 2905–2907 © Thieme Stuttgart · New York