COMMUNICATIONS
4H), 8.84 (brs, 4H), 8.37 (brs, 4H), 7.65 (brs, 4H), 7.41 ppm (brs, 12H);
13C NMR (125 MHz, [D6]DMSO, 258C, TMS): d ¼ 149.2 (d), 141.6 (s),
139.8 (s), 136.7 (d), 136.4 (s), 133.5 (d), 130.8 (d), 129.8 (d), 129.0 (d), 128.7
(s), 127.7 (d), 118.9 (s), 81.3 (s), 76.0 ppm (s); MS (70 eV): m/z (%): 819.3
(100) [Mþ], 136.0 (55).
11: m.p. 138 1408C; IR (CH2Cl2): n˜ ¼ 2960.9, 1596.2, 1369.8, 847.2 cmÀ1
;
1H NMR (500 MHz, CDCl3, 258C, TMS): d ¼ 9.27 (s, 4H), 8.46 (s, 4H), 7.40
(d, J ¼ 8.6 Hz, 4H), 7.03 (s, 4H), 6.91 (s, 4H), 6.75 (d, J ¼ 6.9 Hz, 4H), 3.29
(t, J ¼ 7.1 Hz, 16H), 1.62 1.53 (m, 16H), 1.41 1.32 (m, 16H), 0.96 ppm (t,
J ¼ 7.2 Hz, 24 Hz); 13C NMR (125 MHz, CDCl3, 258C, TMS): d ¼ 150.6 (d),
147.5 (s), 144.3 (s), 134.9 (d), 134.3 (s), 130.6 (d), 127.8 (s), 127.7 (s), 126.5
(d), 120.8 (s), 116.5 (d), 113.5 (d), 81.9 (s), 75.6 (s), 50.7 (t), 29.3 (t), 20.3 (t),
13.9 ppm (q); MS (ES) 1266.5 (1) [Mþ], 579 (1.2), 279.0 (48), 186.1 (100).
12: m.p. > 2508C (decomp); IR (CH2Cl2): n˜ ¼ 2960.9, 1596.2, 1369.8, 847.2,
769.8 cmÀ1
;
1H NMR (500 MHz, CDCl3, 258C, TMS): d ¼ 9.18 (brs, 4H),
Figure 5. Normalized fluorescence spectra of 1 and 11 (n: counts).[24]
8.30 (brs, 4H), 8.08 (brs, 4H), 7.19 (brs, 4H), 6.71 (s, 4H), 6.62 (brs, 4H),
3.21 (brs, 16H), 1.51 (brs, 16H), 1.32 (brs, 16H), 0.92 ppm (brs, 24 Hz);
13C NMR (125 MHz, CDCl3, 258C, TMS): d ¼ 150.0 (d), 148.1 (s), 141.6 (s),
137.8 (s), 134.8 (d), 130.5 (d), 128.9 (s), 127.3 (d), 126.6 (s), 120.5 (s), 115.4
(d), 113.7 (d), 81.9 (s), 75.4 (s), 50.6 (t), 29.6 (t), 20.2 (t), 13.9 ppm (q); MS
(ES) 1328.5 (6) [MþÀPF6], 342.1 (10), 186.2 (24).
Table 1. UV/Vis absorption maxima of phenanthroline compounds and
copper phenanthrolic complexes.
Received: July 9, 2002 [Z19694]
[1]a) G. J. Bodwell, Angew. Chem. 1996, 108, 2221 2224; Angew. Chem.
Int. Ed. Engl. 1996, 35, 2085 2088; b) A. de Meijere, B. Koenig,
Synlett 1997, 1221 1232; c) B. Kˆnig, Top. Curr. Chem. 1998, 196, 92
136; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. 2000,
112, 393 396; Angew. Chem. Int. Ed. 2000, 39, 385 388; e) S. K.
Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189 3192;
f) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2002, 4, 11 14,
and references therein.
[2]P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170 4179.
[3]Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett.
2000, 2, 3265 3268.
[4]K. Campbell, R. McDonald, N. R. Branda, R. R. Tykwinski, Org. Lett.
2001, 3, 1045 1048.
Compound
lmax(abs) [nm]
lmax(em) [nm]
13 (R ¼ H)[25]
440
458
346
410
307 (sh)
473, 553 (sh)
462
383
407
[Cu(13)2]þ (R ¼ H)[26]
[10]
ꢀ
13 (R ¼ C C-Ph)
376, 395
523
416
[10]
ꢀ
13 (R ¼ C C-(p-PhNMe2))
1
2 [Cu(1)2]þ
7 [Cu(6)2]2þ
11
584
12 [Cu(11)2]þ
[5]M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3,
885 887.
copper-complexed core. In addition, resolution of the helical
isomers may be feasible with additional ring substituents and
metal complexation. The synthetic protocol above will
facilitate the preparation of new derivatives that may possess
unusual optical properties, while modification of the acety-
lene spacers offers some control of the helical conformation.
[6]D. R. McMillin, K. M. McNett, Chem. Rev. 1998, 98, 1201 1219.
[7]T. Oyoshi, H. Sugiyama, J. Am. Chem. Soc. 2000, 122, 6313 6314.
[8]S. Otto, J. B. F. N. Engberts, J. Am. Chem. Soc. 1999, 121, 6798 6806.
[9]a) J. W. Madine, X. Wang, R. A. Widenhoefer, Org. Lett. 2001, 3, 385
388; b) L. A. Goj, R. A. Widenhoefer, J. Am. Chem. Soc. 2001, 123,
11133 11147.
[10]H. S. Joshi, R. Jamshidi, Y. Tor, Angew. Chem. 1999, 111, 2888 2891;
Angew. Chem. Int. Ed. 1999, 38, 2722 2725.
[11]F. Ibukuro, M. Fujita, K. Yamaguchi, J.-P. Sauvage, J. Am. Chem. Soc.
1999, 121, 11014 11015.
Experimental Section
Sequential in situ desilylation/dimerization/decomplexation procedure
(11): A solution of tetrabutylammonium fluoride (TBAF) (1m in THF,
1.32 mL, 1.32 mmol, 2.5 equiv) was added in one portion to a stirred
solution of 10 (500 mg, 0.53 mmol, 1 equiv) in pyridine/diethyl ether (3/1,
20 mL). After stirring the solution for 15 min, a solution of Cu(OAc)2
(48 mg, 0.26 mmol, 0.5 equiv) in pyridine/diethyl ether (3/1, 20 mL) was
added over 2.5 h by syringe pump. Once the addition was complete,
additional Cu(OAc)2 (530 mg, 2.92 mmol, 5.5 equiv) was added to the
reaction and the solution turned green immediately. The reaction was
stirred for 18 h at room temperature and partitioned between CH2Cl2 and
water. The aqueous phase was extracted with CH2Cl2 (î 3) and the
combined extracts were washed with KCN (10%, aq) and water, filtered
through celite, and concentrated. Following chromatography on silica gel
(CH2Cl2/MeOH, 30/1), 11 was isolated as an orange solid (130 mg, 39%).
1: m.p. 1508C slow decomp.; 1H NMR (500 MHz, [D6]DMSO, 258C, TMS):
d ¼ 9.33 (brs, 4H), 8.87 (brs, 4H), 7.82 7.77 (m, 12H), 7.63 (brs, 4H),
7.40 ppm (brs, 4H); 13C NMR (125 MHz, [D6]DMSO, 258C, TMS): d ¼
150.4 (d), 144.3 (s), 140.0 (s), 135.9 (d), 133.7 (s), 133.1 (d), 132.3 (d), 131.4
(d), 130.8 (d), 127.7 (s), 126.9 (d), 118.9 (s), 81.4 (s), 76.3 ppm (s); MS (ES)
m/z (%): 757.0 (1), 579.1 (2), 279.0 (4), 141.9 (53).
[12]a) S. Toyota, C. R. Woods, M. Benaglia, R. Haldimann, K. Warnmark,
K. Hardcastle, J. S. Siegel, Angew. Chem. 2001, 113, 773 776; Angew.
Chem. Int. Ed. 2001, 40, 751 754; b) J. C. Loren, J. S. Siegel, Angew.
Chem. 2001, 113, 776 779; Angew. Chem. Int. Ed. 2001, 40, 754 757.
[13]a) S. Sengupta, V. Snieckus, J. Org. Chem. 1990, 55, 5680 5683; b) P.
Knochel, D. Seebach, Tetrahedron Lett. 1982, 23, 3897 3900.
[14]a) D. Tzalis, Y. Tor, S. Failla, J. S. Siegel, Tetrahedron Lett. 1995, 36,
3489 3490; b) Y. Saitoh, T.-A. Koizumi, K. Osakada, T. Yamamoto,
Can. J. Chem. 1997, 75, 1336 1339; c) C. Dietrich-Buchecker, M. C.
Jimenez, J.-P. Sauvage, Tetrahedron Lett. 1999, 40, 3395 3396.
[15]M. Sjoegren, S. Hansson, P. O. Norrby, B. Aakermark, M. E.
Cucciolito, A. Vitagliano, Organometallics 1992, 11, 3954 3964.
[16]M. Kimura, T. Shiba, T. Muto, K. Hanabusa, H. Shirai, Tetrahedron
Lett. 2000, 41, 6809 6813.
[17]a) Templated Organic Synthesis (Eds.: F. Diederich, P. J. Stang),
Wiley-VCH, Weinheim, 2000; b) C. Dietrich-Buchecker, J.-P. Sauv-
age, N. Geum, A. Hori, M. Fujita, S. Sakamoto, K. Yamaguchi, Chem.
Commun. 2001, 1182 1183.
[18]J. J. Pak, T. J. R. Weakley, M. M. Haley, J. Am. Chem. Soc. 1999, 121,
8182 8192.
2: m.p. > 2608C; IR (CH2Cl2): n˜ ¼ 3049.9, 1604.0, 1436.7, 1266.8,
[19]a) R. Berscheid, F. Vˆgtle, Synthesis 1992, 58 62; b) M. Brake, V.
Enkelmann, U. H. F. Bunz, J. Org. Chem. 1996, 61, 1190 1191; c) P.
1119.7 cmÀ1
;
1H NMR (500 MHz, [D6]DMSO, 258C, TMS): d ¼ 9.25 (brs,
4522
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2002, 41, No. 23