was removed by syringe. The lower CF3C6F11 layer was
similarly extracted with cold ether (1.0 ml). The CF3C6F11
layer was recharged with PhMe2SiH (0.219 ml, 1.43 mmol), 11
(0.135 ml, 1.30 mmol), tridecane (0.100 ml, 0.410 mmol) and
ether (2.0 ml). Additional data: see Fig. 4.
from these data (0.0503 g following a 2.000/0.400 volume
correction) was in close agreement with that originally added.
B. A 1 dram vial was charged with 10 (0.1002 g), CF3C6F11
(2.000 ml) and toluene (2.000 ml), capped with a mininert
valve, vigorously shaken (2 min) and immersed (to cap level) in
a 40 1C bath. After 12 h, the sample was allowed to cool to
ambient temperature (24 1C). After 1 h, 0.400 ml aliquots of
each layer were added to stock solutions of decane in hexane
(2.0 ml, 0.0394 M). GC analysis showed 7.77 ꢁ 10ꢀ2 mmol of
10 in the toluene aliquot and 4.543 ꢁ 10ꢀ4 mmol in the
CF3C6F11 aliquot (99.4 : 0.6). The total mass of 10 calculated
from these data (0.1018 g following a 2.000/0.400 volume
correction) was in close agreement with that originally added.
Reduced catalyst loading. In a glove box, a Schlenk flask was
charged with a solution of 1-Rf6 in CF3C6F11 (1.00 ml, 0.0026
M, 0.02 mol%), PhMe2SiH (2.2 ml, 14.4 mmol), 11 (1.35 ml,
13.0 mmol) and hexanes (5.0 ml). The solution was stirred
vigorously at glove box ambient temperature (28 1C). After
72 h, solvents, unreacted 11, and PhMe2SiH were removed by
vacuum. The residue was distilled (Kugelrohr) to give 12 as a
clear oil (2.68 g, 11.4 mmol, 88%, TON ¼ 4400). NMR (d,
CDCl3)22 for 12: 1H, 7.62–7.59 (m, 2H), 7.41–7.27 (m, 3H),
3.63–3.59 (m, 1H), 1.79–1.69 (m, 2H), 1.51–1.50 (m, 2H), 1.35–
1.15 (m, 6H), 0.410 (s, 6H); 13C 133.68, 129.60, 127.94, 71.59,
36.10, 25.72, 24.58, ꢀ0.75.
Acknowledgements
We thank the US Department of Energy (DOE) and the
Bundesministerium fur Bildung und Forschung (BMBF) for
¨
Hydrosilylation rate profiles
support. The initial portion of this study was conducted at the
University of Utah.
Monophasic conditions (CF3C6F11–hexanes, 40 1C; Fig. 5). A
10 ml vial was charged with a solution of 1-Rf6 in CF3C6F11
(1.00 ml, 0.0026 M, 0.20 mol%), PhMe2SiH (0.219 ml, 1.43
mmol), 11 (0.135 ml, 1.30 mmol), hexanes (2.0 ml) and
tridecane (0.100 ml, 0.410 mmol). The vial was heated in a
sand bath with stirring (40 1C). An aliquot (0.001 ml) was
removed every 0.5 h for GC analysis (data in Fig. 5). When
conversion was complete, the sample was cooled to ꢀ30 1C.
After 4 h, the upper hexanes layer was removed by syringe. The
lower CF3C6F11 layer was similarly extracted with cold hex-
anes (1.0 ml). The CF3C6F11 layer was recharged with PhMe2-
SiH (0.219 ml, 1.430 mmol), 11 (0.135 ml, 1.30 mmol), hexanes
(2.0 ml) and tridecane (0.100 ml, 0.410 mmol). The vial
was heated in a sand bath (40 1C) and similarly monitored
by GC. Data, including analogous additional cycles, are given
in Fig. 5.
References
1
2
3
General reference: Handbook of Fluorous Chemistry, eds. J. A.
Gladysz, D. P. Curran and I. T. Horvath, Wiley-VCH, Weinheim,
2004.
J. A. Gladysz and R. C. da Costa, in Handbook of Fluorous
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Wiley-VCH, Weinheim, 2004, pp. 24–40.
(a) I. T. Horvath and J. Rabai, Science, 1994, 266, 72; (b) I. T.
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pp. 5–10.
´
´
´
´
´
´
i
´
´
4
(a) R. C. da Costa and J. A. Gladysz, in Transition Metals for
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Weinheim, 2004, pp. 527–543; (b) See also ch. 10.8–10.14 in ref. 1.
5
6
7
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J. J. J. Juliette, D. Rutherford, I. T. Horva
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D. Rutherford, J. J. J. Juliette, C. Rocaboy, I. T. Horva
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´
th and J. A. Gladysz,
Biphasic conditions (CF3C6F11–toluene, 40 1C; Fig. 6). A 10
ml vial was charged with a solution of 1-Rf6 in CF3C6F11 (1.00
ml, 0.0026 M, 0.20 mol%), PhMe2SiH (0.219 ml, 1.43 mmol),
11 (0.135 ml, 1.30 mmol), toluene (1.0 ml) and tridecane (0.100
ml, 0.410 mmol). The vial was heated in a sand bath with
stirring (40 1C). An aliquot (0.001 ml) was removed every 0.5 h
for GC analysis (data: Fig. 6). When conversion was complete,
the sample was cooled to ambient temperature and the upper
toluene layer removed by syringe. Toluene (1.0 ml) was added
to the lower CF3C6F11 layer. The sample was shaken and the
toluene was removed by syringe. The CF3C6F11 layer was
recharged with PhMe2SiH (0.219 ml, 1.43 mmol), 11 (0.135
ml, 1.30 mmol), toluene (2.0 ml) and tridecane (0.100 ml, 0.410
mmol). The vial was heated in a sand bath (40 1C) and similarly
monitored by GC. Data, including analogous additional
cycles, are given in Fig. 6.
´
th and
L. V. Dinh and J. A. Gladysz, Tetrahedron Lett., 1999, 40
8995.
Reviews covering rhodium-catalyzed hydrosilylations of carbonyl
compounds: (a) H. Brunner, in Transition Metals for Organic
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and New York, 1998, vol. 2, ch. 1.4.2; (b) I. Ojima, Z. Li and
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(a) M. Wende, R. Meier and J. A. Gladysz, J. Am. Chem. Soc.,
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9
10 (a) K. Ishihara, S. Kondo and H. Yamamoto, Synlett., 2001, 1371;
(b) K. Ishihara, A. Hasegawa and H. Yamamoto, Synlett., 2002,
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Partition coefficients
The following are representative.
12 L. V. Dinh and J. A. Gladysz, J. Am. Chem. Soc., submitted.
13 L. V. Dinh, Ph.D. Thesis, University of Utah, Salt Lake City,
Utah, 2004.
14 (a) E. de Wolf, E. A. Speets, B. J. Deelman and G. van Koten,
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A. A 1 dram vial was charged with PhMe2SiH (0.0505 g),
CF3C6F11 (2.000 ml) and toluene (2.000 ml), capped with a
mininert valve, vigorously shaken (2 min) and immersed (to
cap level) in a 40 1C bath. After 12 h, the sample was allowed to
cool to ambient temperature (24 1C). After 1 h, 0.400 ml
aliquots of each layer were added to stock solutions of decane
in hexanes (2.0 ml, 0.0394 M). GC analysis (average of 3
injections) showed 7.127 ꢁ 10ꢀ2 mmol of PhMe2SiH in the
toluene aliquot and 2.647 ꢁ 10ꢀ3 mmol in the CF3C6F11
aliquot (96.4 : 3.6). The total mass of PhMe2SiH calculated
15 (a) J. H. Hildebrand and D. R. F. Cochran, J. Am. Chem. Soc.,
1949, 71, 22; (b) J. A. Gladysz and C. Emnet, in Handbook of
Fluorous Chemistry, eds. J. A. Gladysz, D. P. Curran and I. T.
Horvath, Wiley-VCH, Weinheim, 2004, pp. 11–23.
´
180
N e w J . C h e m . , 2 0 0 5 , 2 9 , 1 7 3 – 1 8 1