C. Walter et al. / Tetrahedron 65 (2009) 5513–5520
5519
4.2.4. (R)-4-Dimethylphenylsilyl-3H-furan-2-one, (R)-11
in the asymmetric unit, hydrogen atoms calculated and refined as
riding atoms.
20
Colorless oil; yield: 39%; [
a
]
ꢁ5.64 (c 0.99, CHCl3); >99% ee.
D
The enantiomeric excess was determined by HPLC using a chiral
column [Chiralpak IB, column temperature 20 ꢀC, n-heptane–i-
PrOH (90:10), 0.8 mL/min, 230 nm, retention times: 15.7 min (R)
4.3.3. X-ray crystal structure analysis for (R)-13
Formula
C17H18O2Si,
M¼282.40,
colorless
crystal
and 18.0 min (S)]. 1H NMR (CDCl3, 300 MHz)
d
0.37 (m, 6H), 2.06 (m,
0.40ꢂ0.30ꢂ0.10 mm, a¼6.3217(1), b¼13.4366(1), c¼9.0172(1) Å,
1H), 2.29 (dd, J¼17.3, 12.6 Hz, 1H), 2.51 (dd, J¼17.2, 8.7 Hz, 1H), 4.11
b
¼104.780(1)ꢀ, V¼740.60(2) Å3, rcalcd¼1.266 g cmꢁ3
,
m
¼1.382 mmꢁ1
,
(dd, J¼11.3, 9.0 Hz, 1H), 4.43 (dd, J¼8.7, 8.7 Hz, 1H), 7.36–7.49 (m,
empirical absorption correction (0.608ꢃTꢃ0.874), Z¼2, monoclinic,
5H). 13C NMR (CDCl3, 75 MHz)
d
ꢁ5.0, ꢁ4.8, 23.9, 30.4, 70.9, 128.1,
space group P21 (no. 4),
l¼1.54178 Å, T¼223(2) K,
u and 4 scans, 4777
130.0, 133.7, 135.2, 178.1. IR (ATR) 1769 cmꢁ1. HRMS (ESI) calcd for
reflections collected (ꢄh, ꢄk, ꢄl), [(sin
q
)/l
]¼0.60 Åꢁ1, 2280 in-
C12H16O2SiNa ([MþNa]þ): 243.0812, found: 243.0818.
dependent (Rint¼0.031) and 2261 observed reflections [Iꢅ2
s(I)], 183
refined parameters, R¼0.036, wR2¼0.097, Flack parameter 0.05(3),
max (min) residual electron density 0.38 (ꢁ0.15) e/Å3, hydrogen
atoms calculated and refined as riding atoms.
4.2.5. (S)-4-Dimethylphenylsilyltetrahydropyran-2-one, (S)-12
20
Colorless oil; yield: 58%; [
a
]
ꢁ36.3 (c 1.0, CHCl3); 98% ee. The
D
enantiomeric excess was determined by HPLC using a chiral col-
umn [Chiralpak AD-H, column temperature 24 ꢀC, n-heptane–i-
PrOH (97:3), 0.8 mL/min, 230 nm, retention times: 19.3 min (S) and
Acknowledgements
20.3 min (R)]. 1H NMR (CDCl3, 300 MHz)
d 0.33 (m, 6H), 1.40 (m,
We thank the Deutsche Forschungsgemeinschaft (Oe 249/3-1)
for research support as well as Solvias AG (Basel/Switzerland) for
the donation of several ligands and Reuter Chemische Appara-
tebau KG for providing an ample supply of (R)-BINOL. Barbara
Hildmann is acknowledged for skillful technical assistance and
Birgit Wibbeling for X-ray measurements. M.O. is indebted to the
Aventis Foundation for a Karl-Winnacker-Stipendium (2006–
2008).
1H), 1.65 (m, 1H), 1.85 (m, 1H), 2.27 (dd, J¼17.4, 12.6 Hz, 1H), 2.57
(ddd, J¼17.4, 5.7, 1.5 Hz, 1H), 4.20–4.33 (m, 2H), 7.33–7.42 (m, 3H),
7.45–7.50 (m, 2H). 13C NMR (CDCl3, 75 MHz)
d
ꢁ5.7, ꢁ5.6, 18.4, 23.7,
30.9, 70.3,128.1, 129.7, 133.9,135.5,171.6. IR (ATR) 1732 cmꢁ1. HRMS
(ESI) calcd for C13H18O2SiNa ([MþNa]þ): 257.0968, found: 257.0953.
4.2.6. (R)-4-Dimethylphenylsilylchroman-2-one, (R)-13
20
Colorless oil; yield: 9%; [
a
]
ꢁ4.30 (c 0.78, CHCl3); 98% ee. The
D
enantiomeric excess was determined by HPLC using a chiral col-
umn [Chiralcel OJ-H, column temperature 20 ꢀC, n-heptane–i-PrOH
(90:10), 0.7 mL/min, 230 nm, retention times: 17.3 min (R) and
References and notes
19.6 min (S)]. 1H NMR (CDCl3, 400 MHz)
d 0.25 (m, 6H), 2.56 (dd,
1. (a) Dieter, R. K. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH:
Weinheim, 2002; pp 79–144; (b) Fleming, I. In Organocopper Reagents.
Practical Approach; Taylor, R. J. K., Ed.; Oxford Academic: New York, NY, 1994;
pp 257–292.
2. Fleming, I. In Science of Synthesis; Fleming, I., Ed.; Thieme: Stuttgart, 2002; Vol.
4, pp 927–946.
3. Diastereoselective conjugate addition of silicon-based cuprates: (a) Oppolzer,
W.; Mills, R. J.; Pachinger, W.; Stevenson, T. Helv. Chim. Acta 1986, 69, 1542–
1545; (b) Fleming, I.; Kindon, N. D. J. Chem. Soc., Chem. Commun. 1987, 1177–
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(f) Dambacher, J.; Bergdahl, M. J. Org. Chem. 2005, 70, 580–589.
4. Oestreich, M.; Weiner, B. Synlett 2004, 2139–2142.
A
J¼7.6, 2.4 Hz, 1H), 2.72 (dd, J¼16.2, 2.4 Hz, 1H), 2.78 (dd, J¼16.2, 7.6,
1H), 6.82 (m, 1H), 6.94 (m, 2H), 7.10 (m, 1H), 7.26–7.37 (m, 5H). 13C
NMR (CDCl3, 100 MHz)
d
ꢁ5.4, ꢁ4.8, 26.2, 30.3, 117.1, 124.1, 125.1,
126.8, 127.7, 128.0, 129.9, 134.0, 135.0, 151.2, 168.8. IR (ATR)
1773 cmꢁ1
282.1076, found: 282.1034.
.
HRMS (ESI) calcd for C17H18O2SiNa ([MþNa]þ):
4.3. X-ray data
4.3.1. General information
5. Auer, G.; Weiner, B.; Oestreich, M. Synthesis 2006, 2113–2116.
6. (a) Suginome, M.; Matsuda, T.; Ohmura, T.; Seki, A.; Murakami, M. In Compre-
hensive Organometallic Chemistry III; Mingos, D. M. P., Crabtree, R. H., Ojima, I.,
Eds.; Elsevier: Oxford, 2007; Vol. 10, pp 725–787; (b) Beletskaya, I.; Moberg, C.
Chem. Rev. 2006, 106, 2320–2354; (c) Suginome, M.; Ito, Y. Chem. Rev. 2000, 100,
3221–3256; (d) Han, L.-B.; Tanaka, M. Chem. Commun. 1999, 395–402.
7. Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am. Chem. Soc. 2002, 124,
5052–5058.
8. Trepohl, V. T.; Oestreich, M. Chem. Commun. 2007, 3300–3302. We had already
proposed this tentative mechanism in connection with a related Si–P bond
activation.
9. (a) Suginome, M.; Matsuda, T.; Ito, Y. Organometallics 2000, 19, 4647–4649; (b)
Ohmura, T.; Masuda, K.; Furukawa, H.; Suginome, M. Organometallics 2007, 26,
1291–1294.
Datasets were collected with a Nonius KappaCCD diffractometer.
Programs used: data collection COLLECT (Nonius B. V., 1998), data
reduction Denzo-SMN,27a absorption correction Denzo,27b structure
solution SHELXS-97,27c structure refinement SHELXL-97,27d graphics
SCHAKL (Universita¨t Freiburg, 1997).
Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publi-
cation. CCDC-700992 [(S)-12] and CCDC-700993 [(R)-13] contain
the supplementary crystallographic data for this paper. These data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: þ44 1223 336–
10. (a) Ohmura, T.; Taniguchi, H.; Suginome, M. J. Am. Chem. Soc. 2006, 128, 13682–
13683; (b) Ohmura, T.; Taniguchi, H.; Kondo, Y.; Suginome, M. J. Am. Chem. Soc.
2007, 129, 3518–3519.
11. Gerdin, M.; Moberg, C. Adv. Synth. Catal. 2005, 347, 749–753.
12. Burks, H. E.; Morken, J. P. Chem. Commun. 2007, 4717–4725.
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known. Cu(I): (a) Ito, H.; Ishizuka, T.; Tateiwa, J.-i; Sonoda, M.; Hosomi, A. J. Am.
Chem. Soc. 1998, 120, 11196–11197; (b) Clark, C. T.; Lake, J. F.; Scheidt, K. A. J. Am.
Chem. Soc. 2004, 126, 84–85; Pd(0): (c) Hayashi, T.; Matsumoto, Y.; Ito, Y. Tet-
rahedron Lett. 1988, 29, 4147–4150; Pd(0)/Me3SiOTf: (d) Ogoshi, S.; Tomiyasu,
S.; Morita, M.; Kurosawa, H. J. Am. Chem. Soc. 2002, 124, 11598–11599; Rh(I): (e)
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14. For the only catalytic asymmetric conjugate silyl transfer by means of a palla-
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Hayashi, T.; Ito, Y. Tetrahedron 1994, 50, 335–346.
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Chem., Int. Ed. 2006, 45, 5675–5677.
4.3.2. X-ray crystal structure analysis for (S)-12
Formula
C13H18O2Si,
M¼234.36,
colorless
crystal,
0.30ꢂ0.25ꢂ0.15 mm, a¼6.6682(4), b¼8.3843(5), c¼12.7971(8) Å,
a
¼77.805(5)ꢀ,
b
¼75.402(1)ꢀ,
g
¼71.187(4)ꢀ, V¼648.75(7) Å3,
rcalcd¼1.200 g cmꢁ3
,
m
¼1.467 mmꢁ1, empirical absorption correc-
tion (0.667ꢃTꢃ0.810), Z¼2, triclinic, space group P1 (no. 1),
l
¼1.54178 Å, T¼223(2) K,
u and 4 scans, 5958 reflections collected
(ꢄh, ꢄk, ꢄl), [(sin
q)/
l
]¼0.60 Åꢁ1, 2719 independent (Rint¼0.036)
and 2607 observed reflections [Iꢅ2
s(I)], 293 refined parameters,
R¼0.062, wR2¼0.173, Flack parameter 0.05(5), max (min) residual
electron density 0.26 (ꢁ0.45) e/Å3, two almost identical molecules