1280
K. Hiroya et al. / Tetrahedron Letters 43 (2002) 1277–1280
OTs
OH
n
n
I
OH
n
TsCl, pyridine
CHCl3, 0˚C - r.t.
PdCl2(PPh3)2, CuI
Et3N, r.t.
NO2
NO2
NO2
23
25a (n=1): 82 %
25b (n=2): 94 %
24a (n=1): 99 %
24b (n=2): 99 %
OTs
n
OTs
n
SnCl2, NaBH4
TsCl, pyridine
CHCl3, 0˚C - r.t.
THF:EtOH (2:1)
NHTs
NH2
26a (n=1): 89 %
26b (n=2): 82 %
27a (n=1): 91 %
27b (n=2): 95 %
n
1) KH
+
2)
50 mol % Cu(OAc)2
dichloroethane, 70˚C
N
Ts
n
N
Ts
OTs
29a (n=1): 0 %
29b (n=2): 14 %
28a (n=1): 67 %
28b (n=2): 64 %
Scheme 1.
compounds using this cyclization reaction are currently
under study in our laboratory.
1994, 50, 11803–11812; (c) Cacchi, S.; Fabrizi, G.; Pace,
P.; Marinelli, F. Synlett 1999, 620–622.
9. (a) Sakamoto, T.; Konodo, Y.; Yamanaka, H. Heterocy-
cles 1986, 24, 31–32; (b) Sakamoto, T.; Konodo, Y.;
Yamanaka, H. Heterocycles 1986, 24, 1845–1847; (c)
Sakamoto, T.; Kondo, Y.; Iwashita, S.; Yamanaka, H.
Chem. Pharm. Bull. 1987, 35, 1823–1828.
10. Yasuhara, A.; Kanamori, Y.; Kaneko, M.; Numata, A.;
Kondo, Y.; Sakamoto, T. J. Chem. Soc., Perkin Trans. 1
1999, 529–534.
References
1. (a) Gribble, G. W. In Comprehensive Heterocyclic Chem-
istry II; Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V.,
Eds.; Pergamon Press: Oxford, 1996; Vol. 2, p. 207; (b)
Gribble, G. W. J. Chem. Soc., Perkin Trans. 1 2000,
1045–1075.
2. (a) Rudisill, D. E.; Stille, J. K. J. Org. Chem. 1989, 54,
5856–5866; (b) Ezquerra, J.; Pedregal, C.; Lamas, C.;
Barluenga, J.; Pe´rez, M.; Garc´ıa-Mart´ın, M. A.; Gonza´-
lez, J. M. J. Org. Chem. 1996, 61, 5804–5812 and refer-
ences cited therein.
3. (a) Kondo, Y.; Kojima, S.; Sakamoto, T. Heterocycles
1996, 43, 2741–2746; (b) Kondo, Y.; Kojima, S.;
Sakamoto, T. J. Org. Chem. 1997, 62, 6507–6511.
4. (a) Yu, M. S.; Leon, L. L.; McGguire, M. A.; Botha, G.
Tetrahedron Lett. 1998, 39, 9347–9350; (b) Sakamoto, T.;
Kondo, Y.; Iwashita, S.; Nagano, T.; Yamanaka, H.
Chem. Pharm. Bull. 1988, 36, 1305–1308.
5. (a) Iritani, K.; Matsubara, S.; Uchimoto, K. Tetrahedron
Lett. 1988, 29, 1799–1802; (b) Arcadi, A.; Cacchi, S.;
Marinelli, F. Tetrahedron Lett. 1989, 30, 2581–2584; (c)
Cacchi, S.; Carnicelli, V.; Marinelli, F. J. Organomet.
Chem. 1994, 475, 289–296; (d) McDonald, F. E.; Chatter-
jee, A. K. Tetrahedron Lett. 1997, 38, 7687–7690; (e)
Rodriguez, A. L.; Koradin, C.; Dohle, W.; Knochel, P.
Angew. Chem., Int. Ed. Engl. 2000, 29, 2488–2490.
6. Cacchi, S.; Fabrizi, G.; Pace, P. J. Org. Chem. 1998, 63,
1001–1011.
11. Only limited number of the examples for unsubstituted
aniline cyclization reaction have been reported. See Refs.
4a and 5.
12. Saulnier, M. G.; Frennesson, D. B.; Deshpande, M. S.;
Vyas, D. M. Tetrahedron Lett. 1995, 36, 7841–7844.
13. Procedure for the tandem cyclization: A solution of 2-
ethynylaniline derivatives (27a or b) in dry dichloroethane
was added to a suspension of KH in dry dichloroethane
at 0°C and the mixture was stirred at the same tempera-
ture for 1 h then at room temperature for 1 h. The
mixture was added to a mixture of Cu(OAc)2 in dry
dichloroethane and was stirred at 70°C for 48 h. Aq.
NH4Cl solution was added and extracted with AcOEt.
The combined organic solution was dried over MgSO4
and the solvent was evaporated. The residue was purified
by silica gel column chromatography to afford the tri-
cyclic compound (28a or b). 28a: 1HNMR (300 MHz,
CDCl3/TMS) l (ppm): 2.31 (3H, s), 2.50 (2H, quint,
J=7.1 Hz), 2.73 (2H, t, J=7.1 Hz), 3.14 (2H, t, J=7.1
Hz), 7.18–7.27 (4H, m), 7.32 (1H, dd, J=7.1 Hz, J=2.1
Hz), 7.72 (2H, d, J=8.5 Hz), 8.02 (1H, dd, J=7.1 Hz,
J=2.1 Hz).; m/z (EI) 311 (M+). HRMS: calcd for
C18H17NO2S: 311.3991. Found: 311.0936. 28b: 1HNMR
(300 MHz, CDCl3/TMS) l (ppm): 1.70–1.95 (4H, m),
2.30 (3H, s), 2.57 (2H, t, J=6.0 Hz), 3.00 (2H, t, J=6.0
Hz), 7.12–7.29 (4H, m), 7.32 (1H, d, J=7.7 Hz), 7.64
(2H, d, J=8.5 Hz), 8.15 (1H, d, J=7.7 Hz).; m/z (EI) 325
(M+). HRMS: calcd for C19H19NO2S: 325.4257. Found:
325.1140.
7. (a) Cacchi, S.; Fabrizi, G.; Marinelli, F.; Moro, L.; Pace,
P. Synlett 1997, 1363–1366; (b) Yasuhara, A.; Kaneko,
M.; Sakamoto, T. Heterocycles 1998, 48, 1793–1799.
8. (a) Arcadi, A.; Cacchi, S.; Carnicelli, V.; Marinelli, F.
Tetrahedron 1994, 50, 437–452; (b) Kondo, Y.; Shiga, F.;
Murata, N.; Sakamoto, T.; Yamanaka, H. Tetrahedron