D
Synlett
Y. Bo, S. McN. Sieburth
Cluster
(
(
8) Tenenbaum, J. M.; Woerpel, K. A. Org. Lett. 2003, 5, 4325.
9) Powell, S. A.; Tenenbaum, J. M.; Woerpel, K. A. J. Am. Chem. Soc.
002, 124, 12648.
10) Fleming, I.; Winter, S. B. D. J. Chem. Soc., Perkin. Trans. 1 1998,
687.
11) Itami, K.; Mitsudo, K.; Yoshida, J.-i. Angew. Chem. Int. Ed. 2001,
0, 2337.
(37) Reagents and solvents were purchased from Aldrich Chemical
Company, Fisher Scientific, Alfa Aesar, or Acros Organics.
Lithium (granular, 99% trace-metals basis) was purchased from
Aldrich (catalogue number: 499811). Most silicon reagents
were purchased from Gelest Inc. Reaction solvents were taken
from a Grubbs-style Solvent Dispensing System purchased from
Glass Contour or they were distilled as described in the litera-
2
(
(
2
4
45
(
(
(
(
12) Li, L.; Navasero, N. Org. Lett. 2004, 6, 3091.
13) James, P.; Landais, Y. Org. Lett. 2004, 6, 325.
ture. Silica gel (60 Å, 170–400 mesh) or basic alumina (50–200
micron, activated) was used for flash column chromatography.
Analytical TLC was performed on Analtech Uniplate Silica Gel GF
(250 micron) precoated glass plates. Spots were detected by UV,
iodine, or phosphomolybdic acid solution.
14) Hernández, D.; Mose, R.; Skrydstrup, T. Org. Lett. 2011, 13, 732.
15) Hernández, D.; Lindsay, K. B.; Nielsen, L.; Mittag, T.; Bjerglund,
K.; Friis, S.; Mose, R.; Skrydstrup, T. J. Org. Chem. 2010, 75, 3283.
16) Nielsen, L.; Skrydstrup, T. J. Am. Chem. Soc. 2008, 130, 13145.
17) Nielsen, L.; Lindsay, K. B.; Faber, J.; Nielsen, N. C.; Skrydstrup, T.
J. Org. Chem. 2007, 72, 10035.
(
(
(38) Herzog, U. J. Prakt. Chem. 2000, 342, 379.
(39) Hosomi, A.; Sakurai, H. Bull. Chem. Soc. Jpn. 1972, 45, 248.
(40) Kashimura, S.; Ishifune, M.; Yamashita, N.; Bu, H.-B.;
Takebayashi, M.; Kitajima, S.; Yoshiwara, D.; Kataoka, Y.;
Nishida, R.; Kawasaki, S.-i.; Murase, H.; Shono, T. J. Org. Chem.
1999, 64, 6615.
(
18) Ballweg, D. M.; Miller, R. C.; Gray, D. L.; Scheidt, K. A. Org. Lett.
2005, 7, 1403.
(
19) Wardell, J. L. In Comprehensive Organometallic Chemistry, Vol. 1;
Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds.; Pergamon:
Oxford, 1982, Chap. 2, 43.
(41) Gilman, H.; Lichtenwalter, G. D. J. Am. Chem. Soc. 1958, 80, 608.
(42) 1,1,1,2-Tetramethyl-2,2-diphenyldisilane (7)
(
(
(
(
20) Gilman, H.; Gorsich, R. D. J. Am. Chem. Soc. 1955, 77, 3134.
21) Gilman, H.; Schwebke, G. L. J. Org. Chem. 1962, 27, 4259.
22) Seyferth, D.; Weiner, M. A. J. Org. Chem. 1961, 26, 4797.
23) George, M. V.; Peterson, D. J.; Gilman, H. J. Am. Chem. Soc. 1960,
Granular Li shot [8 mg, 5.4 mmol, 6 equiv, in mineral oil
(Aldrich)] was washed three times with hexane and transferred
to a 25 mL round-bottomed flask fitted with a septum. The flask
was evacuated and then filled with argon three times. THF (2
mL) was added, and the mixture was cooled to 0 °C. TMSCl (0.1
mL) was then added, the mixture was stirred for 30 min, and
the solution was removed by syringe. The cleaned lithium shot
was washed with THF (3 × 1 mL). A solution of methyl(diphe-
nyl)silane (180 mg, 0.91 mmol) in THF (3 mL) was added, and
the mixture was stirred at 0 °C for 8 h. To this mixture was
added TMSCl (1.5 mL) and, after 5 min, the mixture was concen-
trated. Flash column chromatography (100:1 hexanes–EtOAc)
gave a clear colorless oil; yield: 174 mg (71%).
8
2, 403.
24) Fleming, I.; Roberts, R. S.; Smith, S. C. J. Chem. Soc., Perkin. Trans.
1998, 1209.
25) Sen, S.; Purushotham, M.; Qi, Y.; Sieburth, S. McN. Org. Lett.
007, 9, 4963.
(
(
1
2
(26) Milligan, J. G.; Kraus, C. A. J. Am. Chem. Soc. 1950, 72, 5297.
(27) Gilman, H.; Dunn, G. E. J. Am. Chem. Soc. 1951, 73, 5077.
(28) Bo, Y.; Singh, S.; Duong, H. Q.; Cao, C.; Sieburth, S. McN. Org. Lett.
2011, 13, 1787.
(29) Fleming, I.; Newton, T. W.; Roessler, F. J. Chem. Soc., Perkin.
Trans. 1 1981, 2527.
(43) 1-[3-(Methoxymethoxy)propyl]-2,2,2-trimethyl-1,1-
diphenyldisilane (11)
(
(
30) Brook, A. G.; Gilman, H. J. Am. Chem. Soc. 1954, 76, 278.
31) Gilman, H.; Klein, R. A.; Winkler, H. J. S. J. Org. Chem. 1961, 26,
Granular lithium shot [87 mg, 12.5 mmol, 14 equiv, in mineral
oil (Aldrich)] was washed three times with hexane then trans-
ferred to a 25 mL round-bottomed flask fitted with a septum.
The flask was evacuated and then filled with argon three times.
THF (6 mL) was added, and the mixture cooled to 0 °C. TMSCl
(0.3 mL) was then added, the mixture was stirred for 30 min,
and the solution was removed by syringe. The cleaned lithium
shot was washed with THF (3 × 3 mL). A solution of [3-
(methoxymethoxy)propyl](diphenyl)silane (10; 259 mg, 0.90
mmol) in THF (3.0 mL) was added, and the mixture was stirred
2
474.
32) Fleming, I.; Roberts, R. S.; Smith, S. C. Tetrahedron Lett. 1996, 37,
395.
33) Krempner, C.; Chisholm, M.; Gallucci, J. Angew. Chem. Int. Ed.
008, 47, 410.
34) Gaderbauer, W.; Balatoni, I.; Wagner, H.; Baumgartner, J.;
Marschner, C. Dalton. Trans. 2010, 39, 1598.
35) Zirngast, M.; Flock, M.; Baumgartner, J.; Marschner, C. J. Am.
Chem. Soc. 2009, 131, 15952.
(
(
(
(
(
9
2
for 9 h. The solution was decanted and washed with H O. The
2
36) [Methyl(diphenyl)silyl]lithium from Chloro(methyl)diphe-
nylsilane; Typical Analytical Procedure
aqueous phase was extracted with Et O (3 × 10 mL), and the
2
combined organics were dried (Na SO , filtered, and concen-
2
4
To a round-bottomed flask containing Li shot (41 mg, 5.9 mmol)
under argon, cooled to 0 °C, was added TMSCl (0.1 mL, 0.79
mmol) in THF (2 mL), and the mixture was stirred for 30 min.
The solution was removed by syringe, and the Li was washed
with THF (3 × 1 mL). A solution of chloro(methyl)diphenylsilane
trated. Purification by flash chromatography (gradient 100:1 to
10:1 hexanes–EtOAc) gave a clear, colorless oil; yield: 214 mg
(60%); R = 0.53 (4:1 hexanes–EtOAc).
f
IR (neat): 3067, 2947, 2086, 1954, 1428 cm–1. 1H NMR (400
MHz, CDCl ): δ = 7.45–7.50 (m, 4 H), 7.32–7.37 (m, 6 H), 4.60 (s,
3
(
197 mg, 0.85 mmol) in THF (3.3 mL) was then added dropwise
2 H), 3.50 (t, J = 6.6 Hz, 2 H), 3.34 (s, 3 H), 1.64–1.73 (m, 2 H),
13
to the cleaned lithium shot. At intervals, aliquots (0.2 mL) of the
solution were removed by syringe and added to a round-bottom
flask containing chlorotrimethylsilane (0.1 mL, 0.79 mmol, ca.
1.17–1.24 (m, 2 H), 0.17 (s, 9 H). C NMR (125 MHz, CDCl ):
3
δ = 136.3, 135.4, 128.9, 128.0, 96.5, 70.7, 55.3, 25.1, 9.1, –1.1.
+
HRMS: m/z [M + NH ] calcd for C20H34NO Si : 376.2123; found:
4
2
2
16 equiv) at r.t. After mixing for 5 min, the mixture was concen-
376.2123.
trated in vacuo, taken up in CDCl (1 mL), filtered through
cotton and analyzed by H NMR spectroscopy (see Ref. 44).
(44) Okinoshima, H.; Weber, W. P. J. Organomet. Chem. 1978, 149,
3
1
279.
(45) Armarego, W. L.; Chai, C. L. L. Purification of Laboratory Chemi-
cals, 6th ed.; Butterworth-Heinemann: Oxford, 2009.
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Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–D