Angewandte
Chemie
fluorescence. Studies addressing the synthetic scope of the
domino reaction and the photophysical and pharmacological
properties of these new poly(hetero)cyclic entities are
currently underway.
Experimental Section
9h: To a deaerated mixture of 6 mL of butyronitrile and 6 mL of
triethylamine in an oven-dried screw-cap vessel were added succes-
sively 7b (752 mg, 1.50 mmol), 8g (330 mg, 1.65 mmol),
[PdCl2(PPh3)2] (53 mg, 0.08 mmol), and CuI (14 mg, 0.07 mmol).
This mixture was stirred at room temperature for 2.5 h and then
heated at reflux temperature for 48 h. The reaction mixture was
allowed to cool to room temperature, the solvents were removed in
vacuo, and the residue was chromatographed on silica gel (hexane/
ethyl acetate, 2:1) and crystallized from pentane/diethylether to give
740 mg (86%) of 9h as colorless crystals with blue fluorescence, m.p.
2198C. 1H NMR (500 MHz, CDCl3, 258C, TMS): d = 0.73 (s, 3H;
CH3), 1.21 (s, 3H; CH3), 2.44 (s, 3H; CH3), 3.91 (dd, J = 10.0, 12.4 Hz,
1H; CH), 4.23 (dd, J = 8.7, 12.4 Hz, 1H; CH), 4.53 (dd, J = 8.7, 9.7 Hz,
1H; CH), 6.44 (dd, J = 1.2, 8.3 Hz, 2H; CH), 6.68 (dd, J = 7.5, 8.2 Hz,
2H; CH), 6.90 (tt, J = 1.1, 7.4 Hz, 2H; CHarom.), 7.01 (s, 1H; CHolef.),
7.19 (m, 2H; CHarom.), 7.23 (dd, J = 1.0, 7.6 Hz, 1H; CHarom.), 7.29 (dd,
J = 1.3, 7.6 Hz, 1H; CHarom.), 7.34–7.45 (m, 4H; CHarom.), 7.67 (m, 2H;
CHarom.), 7.85 (d, J = 8.4 Hz, 2H; CHarom.), 8.04 ppm (d, J = 8.2 Hz,
1H; CHarom.); 13C NMR (125 MHz, CDCl3, 258C, TMS): d = 16.8
(CH3), 21.6 (CH3), 21.9 (CH3), 39.9 (Cquat.), 47.7 (CH), 62.3 (Cquat.),
70.2 (CH2), 109.5 (Cquat.), 112.8 (CH), 122.8 (CH), 124.4 (CH), 126.1
(CH), 126.2 (CH), 127.2 (CH), 127.9 (CH), 128.0 (CH), 128.5 (CH),
129.0 (CH), 129.1 (CH), 129.5 (CH), 129.6 (CH), 130.7 (Cquat.), 131.6
(Cquat.), 134.1 (Cquat.), 134.9 (Cquat.), 139.0 (Cquat.), 141.1 (Cquat.), 145.1
(Cquat.), 152.8 (Cquat.), 174.9 ppm (Cquat.); EI MS (70 eV): m/z (%): 573
(M+, 100), 418 (M+ÀSO2C6H4CH3, 32), 267 (10), 201 (10); HRMS
calcd for C36H31NO4S: 573.1974, found: 573.1957; Elemental analysis
calcd for C36H31NO4S (573.7): C 75.37, H 5.45, N 2.44, S 5.59; found: C
75.04, H 5.33, N 2.65, S 5.63.
Figure 2. Fluorescence of the spirocycles 9 f (left) and 9h (right) in
solution (T=298 K, c=10À7 m in CH2Cl2, irradiation at lmax =360 nm).
Received: July 30, 2004
À
Keywords: C C coupling · cycloaddition · domino reactions ·
fluorescence · spiro compounds
.
[1] T. J. J. Müller, M. Ansorge, D. Aktah, Angew. Chem. 2000, 112,
1323 – 1326; Angew. Chem. Int. Ed. 2000, 39, 1253 – 1256.
[2] For lead reviews on Sonogashira couplings, see, for example,
a) S. Takahashi, Y. Kuroyama, K. Sonogashira, N. Hagihara,
Synthesis 1980, 627 – 630; b) K. Sonogashira in Metal-Catalyzed
Cross-Coupling Reactions (Eds.: F. Diederich, P. J. Stang),
Wiley-VCH, Weinheim, 1998, p. 203 – 229; c) K. Sonogashira,
J. Organomet. Chem. 2002, 653(1 – 2), 46 – 49; d) E.-I. Negishi, L.
Anastasia, Chem. Rev. 2003, 103, 1979 – 2018.
Figure 3. Absorption (solid lines, c=10À4 m) and emission spectra
(dotted lines, c=10À7 m) of the spirocycles 9 f (top) and 9h (bottom)
(T=298 K, in CH2Cl2, irradiation at lmax =372 and 358 nm, respec-
tively).
[3] a) T. J. J. Müller, R. Braun, M. Ansorge, Org. Lett. 2000, 2, 1967 –
1970; b) R. U. Braun, K. Zeitler, T. J. J. Müller, Org. Lett. 2000,
2, 4181 – 4184; c) R. U. Braun, K. Zeitler, T. J. J. Müller, Org.
Lett. 2001, 3, 3297 – 3300; d) N. A. M. Yehia, K. Polborn, T. J. J.
Müller, Tetrahedron Lett. 2002, 43, 6907 – 6910; e) O. G. Dediu,
N. A. M. Yehia, T. J. J. Müller, Z. Naturforsch. B 2004, 59, 443 –
450.
[4] For an excellent review on cyclic carbopalladations, see, for
example, E.-I. Negishi, C. CopØret, S. Ma, S.-Y. Liou, F. Liu,
Chem. Rev. 1996, 96, 365 – 393.
[5] For excellent reviews and classifications of domino reactions,
see, for example, a) L. F. Tietze, J. Heterocycl. Chem. 1990, 27,
47 – 69; b) L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137 –
Figure 4. Solid-state fluorescence of single crystals of the spiroindol-
ones 9 f (left) and 9h (right).
Angew. Chem. Int. Ed. 2005, 44, 153 –158
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