[(2S)-2-(Methylsulfonylamino)-2-phenylethyl]diphenylphos-
phine (؉)-2. Yield 40%. δH 2.56 (3 H, s), 2.58 (1 H, ddd, J 13.4,
6.6 and 1.0), 2.68 (1 H, ddd, J 13.9, 8.6 and 1.2), 4.53 (1 H, m),
5.20 (1 H, d, J 5.4), 7.50–7.15 (15 H, m); δC 38.0 (d, J 14.5),
42.0, 56.4 (d, J 17.8), 126.9, 128.4, 128.9 (d, J 7), 129.2, 129.4
(d, J 7), 133.0 (d, J 15.1), 133.1 (d, J 15.1), 141.5 (d, J 5);
δP Ϫ22.8; mp 163–165 ЊC; [α]D ϩ18.6 (c 0.22, CHCl3); HRMS
(FABϩ) Found: m/z, 383.1113. C21H22O2NSP requires m/z,
383.1109.
optical rotation data known from the literature. Absolute
configuration of 10 has not yet been determined.
3-(Diethoxymethylsilyl)cyclohexene 6, cyclohex-2-en-1-ol 7,
2-methylcyclohex-2-en-1-ol 13, 3-(diethoxymethylsilyl)cyclo-
pentene 15, and cyclopent-2-en-1-ol 16 had NMR spectra
in agreement with those reported.13,35,36 1-Butyl-4-(diethoxy-
methylsilyl)cyclohexene 9 was oxidized directly without work-
up to the corresponding alcohol 10.
4-Butylcyclohex-3-en-1-ol 10. [α]D ϩ12.5 (c 0.12, CDCl3);
δH 0.91 (1 H, t, J 7.2), 2.0–1.3 (13 H, m), 4.19 (1 H, m), 5.50
(1 H, m); δC 14.2, 19.3, 22.6, 28.7, 29.9, 32.2, 37.5, 66.1, 123.7,
142.9; HRMS (FABϩ) Found: m/z, 154.1369. C10H18O requires
m/z, 154.1358.
[(2R)-2-(Methylsulfonylamino)-2-phenylethyl]diphenylphos-
phine (Ϫ)-2. The ligand was prepared in 40% yield according to
the general procedure above except using (R)-1 synthesised
from (R)-phenylglycinol and had the same spectroscopic
data as ligand (ϩ)-2. The ligand was used in the preparation of
a racemic mixture of ligand 2. [α]D Ϫ18.4 (c 0.27, CHCl3).
3-(Diethoxymethylsilyl)-2-methylcyclohexene 12. δH 0.13 (s,
3 H), 1.22 (t, 3 H, J 7.0), 1.23 (t, 3 H, J 7.0), 1.99 (br m, 2 H),
1.76 (m, 3 H), 3.79 (q, 2 H, J 7.0), 3.80 (q, 2 H, J 7.0), 5.36 (m,
1 H); δC Ϫ5.0, 18.6, 21.6, 24.2, 24.9, 25.4, 29.6, 58.4, 120.7,
134.5; HRMS (FABϩ) Found: m/z, 228.1544. C12H24O2Si
requires m/z, 228.1546.
[(2S)-2-(Methylsulfonylamino)-2-phenylethyl]diphenylarsine
3. Yield 50%. δH 2.50 (1 H, dd, J 12.7 and 7.4), 2.56 (3 H, s),
2.61 (1 H, dd, J 12.7 and 7.9), 4.66 (1 H, q, J 7.4), 4.97 (1 H, d,
J 7.1), 7.55–7.24 (15 H, m); δC 37.4, 42.0, 57.2, 126.7, 128.5,
128.8, 128.9, 129.0, 129.1, 129.2, 133.1 and 133.3; mp 145–
147 ЊC; [α]D ϩ19.7 (c 0.25, CHCl3); HRMS (FABϩ) Found:
m/z, 427.05823. C21H22O2NSAs requires m/z, 427.05872.
Acknowledgements
We thank the Swedish Natural Science Research Council,
the Crafoord Foundation, the Knut and Alice Wallenberg
Foundation, and the Royal Physiographic Society in Lund for
financial support.
(R)-N-(Methylsulfonyl)-2-phenylaziridine 4
NaH (30 mg, 0.75 mmol, 60% in mineral oil) was added to a
solution of 1 (0.20 g, 0.68 mmol) in THF (10 ml) at rt. The
reaction mixture was heated at 50 ЊC for 4 h. Aqueous work-up
followed by filtration through a short plug of silica afforded
0.11 g, 82% of 4 as a slightly yellow solid. The compound had
the same 1H and 13C spectroscopic data as previously
reported.34 Mp 43–45 ЊC; [α]D Ϫ206.2 (c 0.29, CHCl3); HRMS
(FABϩ) Found: m/z, 198.0581. C9H12O2NS (M ϩ H) requires
m/z, 198.0589.
References
1 L. Pettersson and T. Frejd, J. Chem. Soc., Chem. Commun., 1993,
1823.
2 L. Pettersson, G. Magnusson and T. Frejd, Acta Chem. Scand., 1993,
47, 196.
3 A. Marinetti, Tetrahedron Lett., 1994, 35, 5861.
4 K. Kitayama, H. Tsuji, Y. Uozumi and T. Hayashi, Tetrahedron
Lett., 1996, 37, 4169.
5 G. Pioda and A. Togni, Tetrahedron: Asymmetry, 1998, 9, 3903.
6 H. Ohmura, H. Matsuhashi, M. Tanaka, M. Kuroboshi, T. Hiyama,
Y. Hatanaka and K.-i. Goda, J. Organomet. Chem., 1995, 499,
167.
7 Y. Uozumi and T. Hayashi, J. Am. Chem. Soc., 1991, 113, 9887.
8 T. Okada, T. Morimoto and K. Achiwa, Chem. Lett., 1990, 999.
9 A. Marinetti and L. Ricard, Organometallics, 1994, 13, 3956.
10 T. Hayashi, Y. Matsumoto, I. Morikawa and Y. Ito, Tetrahedron:
Asymmetry, 1990, 1, 151.
Preparation of the catalyst
PdCl2(CH3CN)2 (one equivalent) and the appropriate ligand
(one equivalent) were mixed in benzene and heated at 50 ЊC for
1 h under an argon atmosphere. The solvent was evaporated
under reduced pressure and the resulting yellow–orange powder
was used as catalyst. The catalyst was not rigorously protected
from contact with air.
11 T. Hayashi and Y. Uozumi, Pure Appl. Chem., 1992, 64, 1911.
12 T. Hayashi, Acta. Chem. Scand., 1996, 50, 259.
13 S. Sakuraba, T. Okada, T. Morimoto and K. Achiwa, Chem. Pharm.
Bull., 1995, 43, 927.
14 B. Basu and T. Frejd, Acta. Chem. Scand., 1996, 50, 316.
15 B. Basu, S. K. Chattopadhyay, A. Ritzén and T. Frejd, Tetrahedron:
Asymmetry, 1997, 8, 1841.
16 A. Ritzén, B. Basu, S. K. Chattopadhyay, F. Dossa and T. Frejd,
Tetrahedron: Asymmetry, 1998, 9, 503.
17 A. Ritzén, B. Basu, A. Wållberg and T. Frejd, Tetrahedron:
Asymmetry, 1998, 9, 3491.
18 A. M. Aguiar and T. G. Archibald, J. Org. Chem., 1967, 32, 2627.
19 A. Albinata, F. Lianza, H. Berger, P. S. Pregosin, H. Rüegger and
R. W. Kunz, Inorg. Chem., 1993, 32, 478.
20 V. V. Dunina, E. B. GolovanЈ, N. S. Gulyukina, Y. K. Grishin and
I. P. Beletskaya, Russ. Chem. Bull., 1997, 46, 1331.
21 J. C. Anderson, R. J. Cubbon and J. D. Harling, Tetrahedron:
Asymmetry, 1999, 10, 2829.
22 L. Menabue, M. Saladini and M. Sola, Inorg. Chem., 1990, 29, 1293.
23 L. Menabue and M. Saladini, Inorg. Chem., 1991, 30, 1651.
24 G. Battistuzzi, G. Gavioli, M. Borsari, L. Menabue, M. Saladini and
M. Sola, J. Chem. Soc., Dalton Trans., 1994, 279.
25 G. Battistuzzi, M. Borsari, L. Menabue, M. Saladini and M. Sola,
Inorg. Chim. Acta., 1998, 273, 397.
General procedure for hydrosilylation of substrates 5, 8, 11 and
14 followed by ethanolysis and oxidation
Under an atmosphere of argon the catalyst (0.02 equivalents)
was dissolved in a minimum amount of CH2Cl2. The substrate
(one equivalent) was added and the mixture was cooled to 0 ЊC.
HSiCl2Me (1.5 equivalents) was then added via a syringe and
the mixture was allowed to stir for 40 h at 0 ЊC. The excess of
solvent and hydrosilane was evaporated under reduced pressure
and the resulting crude product was added to a solution of
Et3N in EtOH at 0 ЊC and stirred for 2 h. Pentane was added to
the resulting mixture which was filtered through a small plug of
silica to remove the precipitate. The filtrate was concentrated
under reduced pressure to give the corresponding alkoxysilanes
(for yields, see Table 1).
Oxidation of the alkoxysilanes was performed using a stand-
ard method: KHCO3 (one equivalent), KF (one equivalent) and
H2O2 (one equivalent) were added to the alkoxysilane in
MeOH–THF 1 : 1 at room temperature and then the mixture
was heated at reflux for 5 h. Aqueous work-up and filtration
through a short plug of silica afforded the corresponding alco-
hols in 40–70% yield. The alcohols 7, 10, and 13 were analysed
with respect to the ees using GLC analyses (alpha-DEX
column). The ee of alcohol 16 and the absolute configuration
of alcohols 7, 13 and 16 were determined by comparison of
26 H. Motschi and P. S. Pregosin, Inorg. Chim. Acta., 1980, 40,
141.
27 P. S. Pregosin, R. Rüedi and C. Anklin, Magn. Reson. Chem., 1986,
24, 255.
28 F. H. Allen and A. Pidcock, J. Chem. Soc. (A), 1968, 2700.
1456
J. Chem. Soc., Perkin Trans. 1, 2001, 1452–1457