650
Can. J. Chem. Vol. 83, 2005
-CH2O-), 4.89 (s, 8H, -CH2O-), 0.37 (s, 6H, Si-CH3). 13C
NMR (75 MHz, acetone-d6) δ: 160.6, 160.5, 154.9
(Ar4C4Si), 142.3 (Ar4C4Si), 142.1, 138.3, 138.1, 129.22,
129.18, 128.51, 128.47, 128.3, 128.2, 128.1, 109.8, 108.6,
101.8, 101.4, 70.7 (-CH2O-), 70.4 (-CH2O-), –3.7 (Si-CH3).
29Si NMR (60 MHz, acetone-d6) δ: 8.1. MS (FAB) m/z:
1264 ([M + H]+). Anal. calcd. for C86H74O8Si: C 81.74, H
5.90; found: C 81.58, H 6.15.
125, 1448 (2003); (c) M. Cotlet, R. Gronheid, S. Habuchi, A.
Stefan, A. Barbafina, K. Müllen, J. Hofkens, and F.C.D.
Schryver. J. Am. Chem. Soc. 125, 13 609 (2003); (d) P.-W.
Wang, Y.-J. Liu, C. Devadoss, P. Bharathi, and J.S. Moore.
Adv. Mater. 8, 237 (1996); (e) A.W. Freeman, S.C. Koene,
P.R.L. Malenfant, M.E. Thompson, and J.M.J. Fréchet. J. Am.
Chem. Soc. 122, 12 385 (2000); ( f ) P. Furuta, J. Brooks, M.E.
Thompson, and J.M.J Fréchet. J. Am. Chem. Soc. 123, 13 165
(2003); (g) C.C. Knok and M.S. Wong. Macromolecules, 34,
6821 (2001); (h) S.-C. Lo, N.A.H. Male, J.P.J. Markham, S.W.
Magennis, P.L. Burn, O.V. Salata, and I.D.W. Samuel. Adv.
Mater. 14, 975 (2002); (i) J.P.J. Markham, S.-C. Lo, S.W.
Magennis, P.L. Burn, and I.D.W. Samuel. Appl. Phys. Lett.
80, 2645 (2002).
Synthesis of silole-core dendrimer 3b
A mixture of 2b (502 mg, 0.34 mmol), 1,1,2,2-
tetramethyldisilane (72 mg, 0.60 mmol), and Ni(PEt3)2Cl2
(4 mg, 0.01 mmol) in toluene (10 mL) was heated under re-
flux for 44 h under nitrogen. The mixture was cooled to
room temperature and evaporated. The residue was chro-
matographed over silica gel with toluene–hexane (10:1) to
give 3b (240 mg, 0.081 mmol) as a greenish-yellow glass.
3. (a) A.W. Freeman, L.A.J. Chrisstoffels, and J.M.J. Fréchet. J.
Org. Chem. 65, 7612 (2000); (b) B. Forier and W. Dehaen.
Tetrahedron, 55, 9829 (1999).
4. S. Hecht and J.M.J. Fréchet. J. Am. Chem. Soc. 121, 4084
(1999).
1
Yield 47%. H NMR (300 MHz, acetone-d6) δ: 7.38–7.23
(m, 80H, ArH), 6.65–6.40 (m, 36H, ArH), 5.02–4.74 (m,
48H, -CH2O-), 0.41 (s, 6H, SiCH3). 13C NMR (75 MHz, ac-
etone-d6) δ: 160.92, 160.88, 160.7, 160.4, 154.8 (Ar4C4Si),
142.4 (Ar4C4Si), 142.0, 141.8, 140.6, 140.3, 138.1, 138.0,
129.17, 129.13, 128.53, 128.49, 128.4, 128.1, 108.7, 106.9,
102.1, 101.9, 70.8 (-CH2O-), 70.4 (-CH2O-), 70.3 (-CH2O-),
–3.4 (Si-CH3). 29Si NMR (60 MHz, acetone-d6) δ: 8.1. MS
(MALDI-TOF) m/z: 2984.5 ([M + Na]+). Anal. calcd. for
5. G.V. Wuytswinkel, B. Verheyde, F. Compernolle, S. Toppet,
and W. Dehaen. J. Chem. Soc. Perkin Trans. 1, 1337 (2000).
6. H.C. Kolb, M.G. Finn, and K.B. Sharpless. Angew. Chem. Int.
Ed. 40, 2004 (2001).
7. P. Wu, A.K. Feldman, A.K. Nugent, C.J. Hawker, A. Scheel,
B. Voit, J. Pyun, J.M.J. Fréchet, K.B. Sharpless, and V.V.
Fokin. Angew. Chem. Int. Ed. 43, 3928 (2004).
8. (a) J. Dubac, A. Laporterie, and G. Manuel. Chem. Rev. 90,
215 (1990); (b) J. Dubac, C. Guerin, and P. Meunier. The
chemistry of organic silicon compounds. Vol. 2. Edited by Z.
Rappoport and Y. Apeloig. John Wiley and Sons, New York.
1999. Chap. 34; (c) S. Yamaguchi and K. Tamao. Bull. Chem.
Soc. Jpn. 69, 2327 (1996).
C
198H170O24Si: C 80.30, H 5.79; found: C 79.91, H 5.95.
Synthesis of silole-core dendrimer 3c
mixture of 2c (501 mg, 0.16 mmol), 1,1,2,2-
A
tetramethyldisilane (38 mg, 0.32 mmol), and Ni(PEt3)2Cl2
(6 mg, 0.016 mmol) in toluene (5 mL) was heated under re-
flux for 136 h under nitrogen. The mixture was cooled to
room temperature and evaporated. The residue was
chromatographed over silica gel with CH2Cl2–hexane (2:1)
to give 3c (68 mg, 0.011 mmol) as a greenish-yellow glass.
9. K. Tamao, M. Uchida, T. Izumizawa, K. Furukawa, and S.
Yamaguchi. J. Am. Chem. Soc. 118, 11 974 (1996).
10. (a) S. Yamaguchi, C. Xu, and K. Tamao. J. Am. Chem. Soc.
125, 13 662 (2003); (b) S. Yamaguchi, T. Endo, M. Uchida, T.
Izumizawa, K. Furukawa, and K. Tamao. Chem. Eur. J. 6,
1683 (2000); (c) S. Yamaguchi and K. Tamao. J. Chem. Soc.
Dalton Trans. 3693 (1998); (d) A.J. Boydston, Y. Yin, and B.J.
Pagenkopf. J. Am. Chem. Soc. 126, 3724 (2004); (e) J.
Ohshita, H. Kai, A. Takata, T. Iida, A. Kunai, N. Ohta, K.
Komaguchi, M. Shiotani, A. Adachi, K. Sakamaki, and K.
Okita. Organometallics, 20, 4800 (2000); ( f ) K.-H. Lee, J.
Ohshita, and A. Kunai. Organometallics, 23, 5365 (2004);
(g) J. Luo, Z. Xie, W.Y. Lam, L. Chang, H. Chen, C. Qiu, H.S.
Kwok, X. Zhan, Y. Zhu, and B.Z. Tang. Chem. Commun. 1740
(2001); (h) J. Chen, C.C. Law, J.W.Y. Lam, Y. Dong, S.M.F.
Lo, I.D. Williams, D. Zhu, and B.Z. Tang. Chem. Mater. 15,
1535 (2003); (i) T. Lee, I. Jung, K.-H. Song, H. Lee, J. Choi,
K. Lee, B.J. Lee, J. Park, C. Lee, S.O. Kang, and J. Ko.
Organometallics, 23, 5280 (2004); ( j ) H. Sohn, M.J. Sailor,
D. Magde, and W.C. Trogler. J. Am. Chem. Soc. 15, 3496
(2003).
11. (a) S. Yamaguchi, R.-Z. Jin, and K. Tamao. J. Am. Chem. Soc.
121, 2937 (1999); (b) H. Sohn, R.R. Huddleston, D.P. Powell,
and R. West. J. Am. Chem. Soc. 121, 2935 (1999); (c) T.
Sanji, T. Sakai, C. Kabuto, and H. Sakurai. J. Am. Chem. Soc.
120, 4552 (1998); (d) J. Chen, Z. Xie, J.W.Y. Lam, C.C.W.
Law, and B.Z. Tang. Macromolecules, 36, 1108 (2003); (e) G.
Zhang, J. Ma, and Y. Jiang. Macromolecules, 36, 2130 (2003).
12. (a) D.-L. Jiang and T. Aida. J. Am. Chem. Soc. 120, 10 895
(1998); (b) T. Sato, D.-L. Jing, and T. Aida. J. Am. Chem.
Soc. 121, 10 658 (1999); (c) M.S. Choi, T. Aida, T. Yamazaki,
and I. Yamazaki. Chem. Eur. J. 8, 2667 (2002); (d) C.
1
Yield 13%. H NMR (300 MHz, acetone-d6) δ: 7.32–7.20
(m, 160H, ArH), 6.68–6.36 (m, 84H, ArH), 4.92–4.64 (m,
112H, -CH2O-), 0.38 (s, 6H, Si-CH3). 13C NMR (75 MHz,
acetone-d6) δ: 160.9, 160.8, 140.5, 140.4, 138.0, 129.2,
128.5, 128.4, 107.2, 106.8, 102.0, 70.4 (-CH2O-). 29Si NMR
(60 MHz, acetone-d6) δ: 7.9. MS (MALDI-TOF) m/z: 6465.0
([M + Ag]+). Anal. calcd. for C422H362O56Si: C 79.73, H
5.74; found: C 79.90, H 6.09.
Acknowledgements
This work was partially supported by CREST (Core Re-
search for Evolutional Science and Technology) of JST (Ja-
pan Science and Technology Agency). We also thank the
Ministry of Education, Culture, Sports, Science, and Tech-
nology of Japan (No. 16685004).
References
1. Recent reviews, see: (a) S.M. Grayson and J.M.J. Fréchet.
Chem. Rev. 101, 3819 (2001); (b) G.R. Newkome, E. He, and
C.N. Moorefield. Chem. Rev. 99, 1689 (1999).
2. (a) A. Adronov and J.M.J. Fréchet. Chem. Commun. 1701
(2000); (b) D.W. Brousmiche, J.M. Serin, J.M.J. Fréchet, G.S.
He, T.-C. Lin, S.J. Chung, and P.N. Prasad. J. Am. Chem. Soc.
© 2005 NRC Canada