K. Itami et al.
Bull. Chem. Soc. Jpn., 77, No. 11 (2004) 2079
bined organic phase was dried over MgSO4. Removal of the sol-
vents under reduced pressure and subsequent distillation afforded
14 (5.08 g, 61%) as a colorless liquid: bp 114 ꢁC/1.0 mmHg.
1H NMR (300 MHz) ꢀ 0.45–0.48 (m, 2H), 0.49 (q, J ¼ 7:8 Hz,
6H), 0.88 (t, J ¼ 6:9 Hz, 3H), 0.92 (t, J ¼ 7:8 Hz, 9H), 1.20–
1.30 (m, 20H). 13C NMR (125 MHz) ꢀ 3.4, 7.5, 11.3, 14.1, 22.7,
23.9, 29.4 (two carbons), 29.66, 29.69, 29.73, 29.76, 32.0, 34.0.
HRMS (EI) m=z calcd for C16H35Si [M ꢂ Et]: 255.2508, found
255.2504.
4
a) R. Breslow, Acc. Chem. Res., 24, 159 (1991). b) W.
Blokzijl and J. B. F. N. Engberts, Angew. Chem., Int. Ed. Engl.,
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5
Recent examples: a) C. J. Li and W. C. Zhang, J. Am.
Chem. Soc., 120, 9102 (1998). b) S. Otto, J. B. F. N. Engberts,
and J. C. T. Kwak, J. Am. Chem. Soc., 120, 9517 (1998). c) G.
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Nagayama, and S. Kobayashi, J. Am. Chem. Soc., 122, 7202
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(2000). f) H. Yorimitsu, T. Nakamura, H. Shinokubo, K. Oshima,
K. Omoto, and H. Fujimoto, J. Am. Chem. Soc., 122, 11041
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123, 2919 (2001). h) K. Manabe, X. M. Sun, and S. Kobayashi,
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6
E. Savage, Chem. Rev., 99, 603 (1999). c) D. Broll, C. Kaul, A.
Kramer, P. Krammer, T. Richter, M. Jung, H. Vogel, and P.
¨
Zehner, Angew. Chem., Int. Ed., 38, 2998 (1999). d) M. Siskin
and A. R. Katrinzky, Chem. Rev., 101, 825 (2001). e) A. R.
Katrinzky, D. A. Nichols, M. Siskin, R. Murugan, and M.
Balasubramanian, Chem. Rev., 101, 837 (2001).
1-Dodecyltriisopropylsilane (15). To a suspension of Li (283
mg, 40.8 mmol) in Et2O (8 mL) was added a solution of 1-bromo-
dodecane (5.08 g, 20.4 mmol) in Et2O (8 mL) at 0 ꢁC, and the
ꢁ
mixture was stirred at 0 C for 3 h. To this mixture were added
triisopropylsilyl triflate (6.87 g, 22.4 mmol) and then hexamethyl-
ꢁ
ꢁ
phosphoramide (8 mL) at 0 C. After stirring the mixture at 0 C
for 2 h, and then at room temperature for 15 h, H2O was added to
the reaction mixture and the organic phase was separated. The
aqueous phase was extracted with Et2O (three times) and the com-
bined organic phase was dried over MgSO4. Filtration through a
short silica gel pad (hexane), removal of the solvents under re-
duced pressure, and subsequent distillation afforded 15 (1.51 g,
23%) as a colorless liquid: bp 132 ꢁC/0.9 mmHg. 1H NMR
(300 MHz) ꢀ 0.50–0.60 (m, 2H), 0.88 (t, J ¼ 6:9 Hz, 3H),
0.95–1.00 (m, 3H), 1.02 (s, 18H), 1.20–1.40 (m, 20H). 13C NMR
(125 MHz) ꢀ 9.4, 11.0, 14.1, 18.9, 22.7, 24.3, 29.3, 29.4, 29.68
(two carbons), 29.73, 29.74, 32.0, 34.5. IR (neat) 2959, 2924,
1464, 884, 733, 693, 656 cmꢂ1. HRMS (EI) m=z calcd for
Reviews: a) O. Kajimoto, Chem. Rev., 99, 355 (1999). b) P.
¨
7
a) M. B. Korzenski and J. W. Kolis, Tetrahedron Lett., 38,
5611 (1997). b) Y. Harano, H. Sato, and F. Hirata, J. Am. Chem.
Soc., 122, 2289 (2000).
8
a) A. R. Katritzky, S. M. Allin, and M. Siskin, Acc. Chem.
Res., 29, 399 (1996). b) K. Chandler, F. Deng, A. K. Dillow, C. L.
Liotta, and C. A. Eckert, Ind. Eng. Chem. Res., 36, 5175 (1997).
i
C18H39Si [M ꢂ Pr]: 283.2821, found 283.2813. Anal. Calcd for
C21H46Si: C, 77.21; H, 14.19%. Found: C, 77.04; H, 14.45%.
Tetra(1-dodecyl)silane (16). To a suspension of Li (304 mg,
43.8 mmol) in Et2O (10 mL) was added a solution of 1-bromodo-
decane (5.51 g, 22.1 mmol) in Et2O (10 mL) at 0 ꢁC, and the mix-
9
a) B. Kuhlmann, E. M. Arnett, and M. Siskin, J. Org.
Chem., 59, 5377 (1994). b) J. An, L. Bagnell, T. Cablewski,
C. R. Strauss, and R. W. Trainor, J. Org. Chem., 62, 2505
(1997). c) Y. Ikushima, K. Hatakeda, O. Sato, T. Yokoyama,
and M. Arai, J. Am. Chem. Soc., 122, 1908 (2000).
10 H. Oka, S. Yamago, J. Yoshida, and O. Kajimoto, Angew.
Chem., Int. Ed., 41, 623 (2002).
ꢁ
ture was stirred at 0 C for 5 h. To this mixture was added tetra-
ꢁ
chlorosilane (538 mg, 3.17 mmol) at 0 C. After stirring the mix-
ꢁ
ture at 0 C for 1 h and then at room temperature for 70 h, H2O
was added to the reaction mixture and the organic phase was sep-
arated. The aqueous phase was extracted with Et2O (three times)
and the combined organic phase was dried over MgSO4. Removal
of the solvents under reduced pressure, and subsequent gel perme-
ation chromatography afforded 16 (1.81 g, 81%) as colorless oil.
1H NMR (300 MHz) ꢀ 0.40–0.50 (m, 8H), 0.88 (t, J ¼ 7:2 Hz,
12H), 1.20–1.35 (br, 80H). 13C NMR (125 MHz) ꢀ 12.5, 14.1,
22.7, 23.9, 29.34, 29.40, 29.66, 29.70, 29.74, 29.76, 32.0, 33.9.
IR (neat) 2922, 2853, 1466, 766, 722 cmꢂ1. HRMS (EI) m=z calcd
for C36H75Si [M ꢂ C12H25]: 535.5638, found 535.5637.
11 a) P. Reardon, S. Metts, C. Crittendon, P. Daugherity, and
E. J. Parsons, Organometallics, 14, 3810 (1995). b) J. Diminnie,
S. Metts, and E. J. Parsons, Organometallics, 14, 4023 (1995).
12 M. A. Brook, ‘‘Silicon in Organic, Organometallic, and
Polymer Chemistry,’’ John Wiley & Sons, New York (2000).
13 a) K. Itami, K. Mitsudo, and J. Yoshida, J. Org. Chem., 64,
8709 (1999). b) K. Itami, T. Nokami, and J. Yoshida, Org. Lett., 2,
1299 (2000). c) K. Itami, K. Mitsudo, T. Kamei, T. Koike, T.
Nokami, and J. Yoshida, J. Am. Chem. Soc., 122, 12013 (2000).
d) K. Itami, T. Nokami, and J. Yoshida, J. Am. Chem. Soc.,
123, 5600 (2001). e) K. Itami, T. Koike, and J. Yoshida, J. Am.
Chem. Soc., 123, 6957 (2001). f) K. Itami, T. Kamei, and J.
Yoshida, J. Am. Chem. Soc., 123, 8773 (2001). g) K. Itami, K.
Mitsudo, and J. Yoshida, Angew. Chem., Int. Ed., 40, 2337
(2001). h) K. Itami, T. Kamei, K. Mitsudo, T. Nokami, and J.
Yoshida, J. Org. Chem., 66, 3970 (2001). i) K. Itami, T. Nokami,
Y. Ishimura, K. Mitsudo, T. Kamei, and J. Yoshida, J. Am. Chem.
Soc., 123, 11577 (2001). j) K. Itami, K. Mitsudo, A. Nishino, and
J. Yoshida, J. Org. Chem., 67, 2645 (2002). k) K. Itami, K.
Mitsudo, and J. Yoshida, Angew. Chem., Int. Ed., 41, 3481
(2002). l) K. Itami, K. Mitsudo, T. Nokami, T. Kamei, T. Koike,
and J. Yoshida, J. Organomet. Chem., 653, 105 (2002). m) K.
Itami, M. Mineno, T. Kamei, and J. Yoshida, Org. Lett., 4, 3635
(2002). n) K. Itami, T. Kamei, M. Mineno, and J. Yoshida, Chem.
Lett., 2002, 1084. o) K. Itami, T. Kamei, and J. Yoshida, J. Am.
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This work was supported by CREST of Japan Science and
Technology Corporation. We thank Dr. Hiroyuki Oka for tech-
nical assistance and valuable suggestions.
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