LETTER
Aminations of Pyrimidines, Triazines and Tetrazines
2141
Table 3 Synthesis of Derivatives 22 and 23a
OMe
OMe
Pd-catalyzed
reaction
(Het)Ar
+
(Het)Ar-SMe
(Het)ArSMe
SMe
N
H
H2N
1.2 equiv
9–13
Entry
1
Product
Yield (%)
OMe
ND
N
H
OMe
N
N
2
3
4
5
ND
N
H
SMe
N
N
OMe
N
ND
N
H
N
SMe
OMe
N
N
N
22 (73%)
N
N
H
N
SMe
N
MeS
N
OMe
MeS
N
N
23 (88%)
N
N
N
N
SMe
H
a For reaction conditions see Table 1, entry 7.
b ND: not detected.
(8) (a) Jacobsen, N. W.; De Jonge, I. Aust. J. Chem. 1987, 40,
1979. (b) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K.
Tetrahedron 2000, 56, 1165. (c) Keen, S. P.; Cowden, C. J.;
Bishop, B. C.; Brands, K. M. J.; Davies, A.; Dolling, U. H.;
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1771. (d) Ethel Garnier, E.; Audoux, J.; Pasquinet, E.;
Suzenet, F.; Poullain, D.; Lebret, B.; Guillaumet, G.
J. Org. Chem. 2004, 69, 7809.
(9) (a) Taylor, E. C.; Macor, J. E. J. Org. Chem. 1989, 54, 1249.
(b) Azev, Y.; Lork, E.; Duelcks, T.; Gabel, D. Tetrahedron
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(10) Pitts, W. J.; Guo, J.; Dhar, T. G. M.; Shen, Z.; Gu, H. H.;
Watterson, S. H.; Bednarz, M. S.; Chen, B.-C.; Barrish, J. C.;
Bassolino, D.; Cheney, D.; Fleener, C. A.; Rouleau, K. A.;
Hollenbaugh, D. L.; Iwanowicz, E. J. Bioorg. Med. Chem.
Lett. 2002, 12, 2137.
(11) (a) Neunhoeffer, H.; Wiley, P. F. In Chemistry of 1,2,3-
Triazines and 1,2,4-Triazines, Tetrazines and Pentazines;
Weissberger, A.; Taylor, E. C., Eds.; Wiley: New York,
1974, 409. (b) Emilson, H. J. Heterocycl. Chem. 1989, 26,
1077.
(12) (a) Wolfe, J. P.; Wagaw, S.; Buchwald, S. L. J. Am. Chem.
Soc. 1996, 118, 7215. (b) Wolfe, J. P.; Buchwald, S. L.
J. Org. Chem. 1996, 61, 1133. (c) Shekhar, S.; Ryberg, P.;
Hartwig, J. F.; Mathew, J. S.; Blackmond, D. G.; Strieter,
E. R.; Buchwald, S. L. J. Am. Chem. Soc. 2006, 128, 3584.
(13) General Procedure for the Heterocyclic Amination: In a
sealed microwave vial were successively added the SMe
derivative, the amine (1.2 equiv), copper(I) methylsalicylate
(2.0 equiv), Cs2CO3 (2.2 equiv), Pd(OAc)2 (10 mol%) and
xantphos (20 mol%). Anhydrous toluene was added and the
suspension was subjected to MW irradiation at 170 °C for 2
h. The reaction mixture was cooled to r.t. and the solvent was
References and Notes
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(5) (a) Alphonse, F.-A.; Suzenet, F.; Keromnes, A.; Lebret, B.;
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Routier, S.; Akssira, M.; Leger, J.-M.; Jarry, C.; Guillaumet,
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Synlett 2009, No. 13, 2137–2142 © Thieme Stuttgart · New York