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3880
M. Die´guez et al. / Tetrahedron: Asymmetry 16 (2005) 3877–3880
3
3
0
(dd, 1H, H-5, J5-5 = 12.8 Hz, J5-4 = 8.4 Hz), 3.25 (dd,
(Ramon y Cajal fellowship to O.P.) and the Generalitat
de Catalunya (Distinction to M.D.). We thank under-
graduate Silvia Serres for her fruitful collaboration.
1H, H-50, J5 -5 = 12.8 Hz, 3J5 -4 = 6.4 Hz), 4.37 (m, 1H,
H-4), 4.52 (dd, 1H, H-3, J3-P = 10 Hz, J3-4 = 2.8 Hz),
3
0
0
3
3
3
4.61 (d, 1H, H-2, J2-1 = 4 Hz), 5.96 (d, 1H, H-1,
3J1-2 = 4 Hz), 7.1–7.6 (m, 14H, CH@). 13C NMR
(CDCl3), d: 26.5 (CH3), 27.0 (CH3), 30.7 (C-5), 79.1
References
3
2
(d, C-4, J4-P = 6.8 Hz), 82.7 (d, C-3, J3-P = 20.6 Hz),
84.1 (d, C-2, J4-P = 5.5 Hz), 105.2 (C-1), 112.4
(CMe2), 125–132 (aromatic carbons). Anal. Calcd (%)
for C27H26F3O4PS: C, 60.67; H, 4.90; S, 6.00. Found:
C, 60.97; H, 4.92; S, 5.98.
3
1. For reviews, see for instance: (a) Noyori, R. Asymmetric
Catalysis in Organic Synthesis; Wiley: New York, 1994; (b)
Catalytic asymmetric synthesis; Ojima, I., Ed.; Wiley-
VCH: New York, 2000; (c) Comprehensive Asymmetric
Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H.,
Eds.; Springer: Berlin, 1999; Vol 1.
2. (a) Hiraoka, M.; Nishikawa, A.; Morimoto, T.; Achiwa,
K. Chem. Pharm. Bull. 1998, 46, 704; (b) Nishibayashi, Y.;
Segawa, K.; Singh, J. D.; Fukuzawa, S.; Ohe, K.; Uemura,
S. Organometallics 1996, 15, 370.
4.6. 1,2-O-Isopropylidene-3-diphenylphosphinite-5-(2,6-
dimethylphenyl)sulfanyl-D-xylofuranose 7
Yield: 0.67 g (68%). 31P NMR, d: 115.6 (s). H NMR
(CDCl3), d: 1.26 (s, 3H, CH3), 1.39 (s, 3H, CH3),
1
3. Evans, D. A.; Michael, F. E.; Tedrow, J. S.; Campos,
K. R. J. Am. Chem. Soc. 2003, 125, 3534.
3
0
2.51 (s, 6H, CH3-Ph), 2.82 (dd, 1H, H-5, J5-5
=
=
3
3
10.4 Hz, J5-4 = 6 Hz), 2.90 (dd, 1H, H-50, J5 -5
0
´
`
4. For reviews, see: (a) Dieguez, M.; Pamies, O.; Claver, C.
3
0
10.4 Hz, J5 -4 = 7.2 Hz), 4.13 (m, 1H, H-4), 4.46 (dd,
1H, H-3, J3-P = 9.2 Hz, J3-4 = 2.4 Hz), 4.58 (d, 1H,
´
`
Chem. Rev. 2004, 104, 3189; (b) Dieguez, M.; Pamies, O.;
3
3
´ ´
Ruiz, A.; Dıaz, Y.; Castillon, S.; Claver, C. Coord. Chem.
3
3
´
Rev. 2004, 248, 2165; (c) Dieguez, M.; Ruiz, A.; Claver, C.
H-2, J2-1 = 3.6 Hz), 5.91 (d, 1H, H-1, J1-2 = 3.6 Hz),
7.0–7.5 (m, 13H, CH@). 13C NMR (CDCl3), d: 22.1
(CH3-Ph), 26.5 (CH3), 26.7 (CH3), 33.0 (C-5), 79.8 (d,
C-4, J4-P = 6.1 Hz), 82.4 (d, C-3, J3-P = 18.3 Hz),
83.9 (C-2), 104.9 (C-1), 111.9 (CMe2), 125–144 (aro-
matic carbons). Anal. Calcd (%) for C28H31O4PS: C,
68.00; H, 6.32; S, 6.48. Found: C, 67.97; H, 6.34; S, 6.53.
Dalton Trans. 2003, 2957.
5. (a) Haag, D.; Runsink, J.; Schaf, H. D. Organometallics
1998, 17, 398; (b) Heldmann, D. K.; Seebach, D. Helv.
Chim. Acta 1999, 82, 1096.
3
2
`
´
6. See for instance: (a) Pamies, O.; Dieguez, M.; Net, G.;
Ruiz, A.; Claver, C. Tetrahedron: Asymmetry 2000, 11,
´
4377; (b) Dieguez, M.; Ruiz, A.; Claver, C. Tetrahedron:
´
`
Asymmetry 2001, 12, 2895; (c) Dieguez, M.; Pamies, O.;
4.7. General procedure for asymmetric hydrosilylation
reactions
´
Ruiz, A.; Castillon, S.; Claver, C. Tetrahedron: Asymmetry
`
´
2000, 11, 4701; (d) Pamies, O.; Dieguez, M.; Ruiz, A.;
´
Claver, C. J. Org. Chem. 2001, 66, 8364; (e) Dieguez, M.;
Ruiz, A.; Claver, C. Chem. Commun. 2001, 2702; (f)
To
a solution of the desired catalyst precursor
´
`
´
Dieguez, M.; Pamies, O.; Ruiz, A.; Castillon, S.; Claver,
(0.01 mmol Rh) in the corresponding solvent (2 mL),
the ligand (0.011 mmol) was added. The mixture was
stirred for 30 min. Ketone (1 mmol), Ph2SiH2
(1.1 mmol) and undecane as the GC internal standard
(0.1 mL) were then added. After the desired reaction
time, the reaction mixture was quenched with methanol
(7 mL) and 2.5 M aqueous NaOH (5 mL). The mixture
was extracted with diethyl ether (3 · 5 mL), the com-
bined ether phases were dried over Na2SO4 and filtered.
The conversion and enantiomeric excesses were deter-
mined by GC.
´
`
C. Chem. Eur. J. 2001, 7, 3086; (g) Dieguez, M.; Pamies,
O.; Ruiz, A.; Claver, C. New. J. Chem. 2002, 26, 827; (h)
RajanBabu, T. V.; Ayers, T. A.; Halliday, G. A.; You, K.
K.; Calabrese, J. C. J. Org. Chem. 1997, 62, 6012; (i)
Reetz, M. T.; Neugebauer, T. Angew. Chem., Int. Ed.
1999, 38, 179; (j) Yonehara, K.; Hashimuze, T.; Mori, K.;
Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 9374.
7. The preparation of ligands 1–3 is reported in Guimet, E.;
´
Dieguez, M.; Ruiz, A.; Claver, C. Tetrahedron: Asymme-
try 2005, 16, 959.
8. Thioether-alcohols are easily prepared on a large scale
from D-(+)-xylose using the standard procedure described
`
´
in Pamies, O.; Dieguez, M.; Net, G.; Ruiz, A.; Claver, C.
Organometallics 2000, 19, 1488.
Acknowledgements
9. This behavior is similar to that observed by Evans et al.3
when using phosphinite–thioether ligand 10.
10. Giordano, C.; Crabtree, R. H. Inorg. Synth. 1979, 19, 218.
11. Green, M.; Kuc, T. A.; Taylor, S. H. J. J. Chem. Soc. A
1971, 2334.
This work was supported by the Spanish Ministerio de
´
Educacion, Cultura
y
Deporte (CTQ2004-04412/
BQU), the Spanish Ministerio de Ciencia y Tecnologia