M. Omote et al. / Journal of Organometallic Chemistry 611 (2000) 20–25
25
CH3), 7.24–7.53 (m, 15H, ArH). MS (m/z): 374 [M+
(weak)], 197 (SiMe(Ph)2), 177 (SiBuMePh), 121
(SiMePh). Found: m/z 374.1906. Calc. for C24H30Si2:
M, 374.1886.
(S)-8 were evaluated as methyl(1-naphthyl)phenylsilane
after hydrolysis.
Methyl(1-naphthyl)phenylsilane: Found: m/z 248.
1026. Calc. for C17H16Si: M, 248.1021.
4.2.3. (R)-Methyl(1-naphthyl)phenylsilyltri-
methylstannane [(R)-6]
Acknowledgements
In a flask (S)-1 (1.13 g, 4.0 mmol) was dissolved in 5
ml of Et2O and 5 ml of pentane. To the solution,
trimethylstannyllithium in THF (0.5 M solution, 5.0
mmol) was added dropwise for 1 h at −20°C under
stirring. After decomposition by a phosphate buffer
solution, the products were extracted with Et2O (3×30
ml) and purified by silica-gel column chromatography
(10:1 hexane–toluene) to afford (R)-6 (0.88 g, 54%
yield).
This work was partially supported by a Grant-in-Aid
for Scientific Research (11450354), and a Grant-in-Aid
for Scientific Research in Priority Areas, The Chemistry
of Inter-element Linkage (11120221) from the Ministry
of Education, Science, Sports, and Culture of Japan.
The authors are also grateful to Shin-Etsu Chemical
Co., Ltd. for the generous donation of organosilicon
compounds.
1H-NMR: l 0.10 (s, 9H, SnCH3), 0.88 (s, 3H,
SiCH3), 7.32–7.90 (m, 12H, ArH). MS (m/z): 412, 410,
408 [M+ (weak)], 397, 395, 393 [M-15(Me)], 247
(SiMeNpPh), 135, 133, 131 (SnMe). Found: m/z
412.0667. Calc. for C20H24SiSn: M, 412.0669.
The tri(n-butyl) analogue was obtained similarly
(2.29 g, 50% yield).
References
[1] Y. Kawakami, K. Takeyama, K. Komuro, O. Ooi, Macro-
molecules 31 (1998) 551.
[2] Y. Kawakami, T. Takahashi, Y. Yada, I. Imae, Polym. J. 30
(1998) 1001.
[3] Y. Kawakami, K. Nakao, S. Shinke, I. Imae, Macromolecules 32
(1999) 6874.
[4] Y. Li, Y. Kawakami, Macromolecules 31 (1998) 5592.
[5] Y. Li, Y. Kawakami, Macromolecules 32 (1999) 548.
[6] M. Murano, Y. Li, Y. Kawakami, Macromolecules 33 (2000)
3940.
[7] M. Oishi, Y. Kawakami, Org. Lett. 1 (1999) 549.
[8] M. Oishi, Y. Kawakami, Macromolecules 33 (2000) 1960.
[9] (a) H. Gilman, G.D. Lichtenwalter, J. Am. Chem. Soc. 80 (1958)
607. (b) M.V. George, D.J. Peterson, H. J. Gilman, J. Am.
Chem. Soc. 82 (1960) 403.
1H-NMR: l 0.74 (t, 3H, J=7.1 Hz, SnC3H6CH3),
0.87 (t, 2H, J=7.3 Hz, SnCH2C3H7), 0.89 (s, 3H,
SiCH3), 1.15 (seq, 2H, J=7.3 Hz, SnC2H4CH2CH3),
1.32 (quin, 2H, J=7.3 Hz, SnCH2CH2C2H5), 7.29–
7.91 (m, 12H, ArH). MS (m/z): 481, 479, 477 [M-
57(Bu) (weak)], 425, 423, 421 ([M+H]-113 (Bu2)
[weak]), 369, 367, 365 ([M+H2]-171 (Bu3) [weak]), 247
(SiMeNpPh), 121, 119, 117 (Sn+H).
[10] A.J. Chalk, J.F. Harrod, J. Am. Chem. Soc. 89 (1967) 1640.
[11] E. Hengge, N. Holtschmid, J. Organomet. Chem. 12 (1968) 5.
[12] W.C. Still, J. Org. Chem. 41 (1976) 3063.
[13] G. Bu¨chi, H. Wu¨est, J. Org. Chem. 44 (1979) 546.
[14] J.-K. Choi, D.J. Hart, Y.-M. Tsai, Tetrahedron Lett. 23 (1982)
4765.
[15] (a) K. Tamao, A. Kawachi, Angew. Chem. Int. Ed. Engl. 34
(1995) 818. (b) A. Kawachi, K. Tamao, Bull. Chem. Soc. Jpn. 70
(1997) 945 and Refs. cited therein.
4.2.4. (n-Butyl)methylphenylsilyllithium (7)
In a flask were placed finely cut lithium (0.11 g, 15
mmol), dry THF (10 ml) under argon. (R)-3 (0.26 g, 0.7
mmol) was added and the reaction system was stirred at
−8°C for 36 h. The extent of the formation of 7 was
evaluated as (n-butyl)methylphenylsilane after hydroly-
sis with 1 N HCl. The stereochemistry was studied by
HPLC after conversion of the silane into 2 via chlorina-
tion and alkylation by 1-naphthyllithium.
[16] K. Ikenaga, Abstract of the 3rd Symposium on the ‘Chemistry of
the Inter-element Linkage’ (Grant-in-Aid for Scientific Research
on Priority Area) (Japanese), 1998, p. 41.
[17] L.H. Sommer, C.L. Frye, G.A. Parker, K.W. Michael, J. Am.
Chem. Soc. 86 (1964) 3271.
[18] E. Colomer, R.J.P. Corriu, J. Chem. Soc. Chem. Commun.
(1976) 176.
[19] E. Colomer, R.J.P. Corriu, J. Organomet. Chem. 133 (1977) 159.
[20] C. Tamborski, F.E. Ford, E.J. Soloski, J. Org. Chem. 28 (1963)
273.
4.2.5. (R)-methyl(1-naphthyl)phenylsilyllithium [(S)-8]
To methyllithium (1.5 mmol) in THF (20 ml) kept at
−78°C under argon atmosphere, (R)-6 (412 mg, 1
mmol) in a solvent (20 ml) was added dropwise for 2 h.
The extent of the formation and the stereochemistry of
.