966
LETTERS
SYNLETT
(3) a) Soai, K.; Niwa, S. Chem. Rev. 1992, 92, 833. b) Noyori, R.;
Kitamura, M. Angew. Chem. Int. Ed. Engl. 1991, 30, 49.
(4) Cozzi, P. G.; Papa, A.; Umani-Ronchi, A. Terahedron Lett. 1996,
37, 4613.
(5) Suzuki, T.; Hirokawa, Y.; Ohtake, K.; Shibata, T.; Soai, K.
Terahedron: Aymmetry 1997, 8, 4033.
(6) Itsuno, S.; Sakurai, Y.; Ito, K.; Maruyama, T.; Nakahama, S,
Fréchet, J. M. J. J. Org. Chem. 1990, 55, 304.
(7) Mino, T.; Saitoh, M.; Yamashita, M. J. Org. Chem. 1997, 62,
3981.
(8) Enders, D.; Kirchhoff, J. Acros Organics Acta 1996, 2, 10 and
references cited therein.
(9) Enders, D.; Breuer, K.; Runsink, J. Helv. Chem. Acta 1996, 79,
1899.
25
1
(10) 1. [α]
=+25.48 (c 1.0, CHCl ); m.p. 144–145 8C; H NMR
3
D
(CDCl ) δ: 1.64 (s, 3H), 1.65 (s, 3H), 3.55 (d, J=2.4 Hz, 1H), 3.97
3
(dd, J=2.4 and 12.2 Hz, 1H), 4.47 (dd, J=3.1 and 12.2 Hz, 1H),
13
5.33 (d, J=2.4 Hz, 1H), 7.10–7.99 (m, 9H), 8.52 (s, 1H); C NMR
(CDCl ) δ: 19.52, 29.08, 64.97, 67.24, 74.17, 99.53, 121.33,
3
124.59, 126.73, 127.32, 127.90, 136.32, 138.85, 148.99, 154.52,
+
163.00; MS m/z (rel intensity): 281 (M -Me, 0.4).
25
1
2. [α] =+28.68 (c 1.0, CHCl ); m.p. 121–122 8C; H NMR
D
3
(CDCl ) δ: 1.64 (s, 3H), 1.65 (s, 3H) , 2.50 (s, 3H), 3.55 (q, J=2.7
3
Hz, 1H), 3.93 (dd, J=2.4 and 12.2 Hz, 1H), 4.45 (dd, J=3.0 and
12.2 Hz, 1H), 5.33 (d, J=2.4 Hz, 1H), 7.09–7.80 (m, 8H), 7.97 (s,
13
1H); C NMR (CDCl ) δ: 19.58, 24.23, 29.05, 65.01, 67.63,
3
74.18, 99.54, 118.45, 124.22, 126.81, 127.28, 127.89, 136.57,
+
138.89, 153.96, 157.55, 163.19; MS m/z (rel intensity): 310 (M ,
100).
3. [α]
25
1
=+39.48 (c 1.0, CHCl ); m.p. 180–182 8C;
H
D
3
NMR(CDCl ) δ: 1.62 (s, 3H), 1.64 (s, 3H) , 3.39 (d, J=2.0 Hz,
3
1H), 3.97 (dd, J=2.0 and 7.8 Hz, 1H), 4.45 (dd, J=2.4 and 12.2 Hz,
1H), 5.31 (d, J=2.0 Hz, 1H), 6.73–7.87 (m, 9H), 7.89 (s, 1H); MS
was added. After 20 min, diethylzinc (2 mmol, 2 mL of 1 M solution in
hexane) was added and stirring was continued for 1 h. After warming to
-35° C, benzaldehyde (1.0 mmol, 0.10 mL) was added and the mixture
was stirred for 24 h at -35° C. The reaction mixture was quenched with 2
M hydrochloric acid, and then extracted with ether. The organic layers
+
m/z (rel intensity): 311 (M , 1.5).
25
1
4. [α]
=+37.88 (c 1.0, CHCl ); m.p. 107–109 8C; H NMR
3
D
(CDCl ) δ: 1.42 (s, 9H), 1.62 (s, 3H), 1.64 (s, 3H) , 3.37 (q, J=2.1
3
Hz, 1H), 3.99 (dd, J=2.1 and 11.9 Hz, 1H), 4.45 (dd, J=2.4 and
were washed with sat. NaHCO aq. and brine, and dried over MgSO
3
4
11.9 Hz, 1H), 5.30 (d, J=2.4 Hz, 1H), 6.66–7.28 (m, 8H), 7.93 (s,
anhydrous. The solvent was evaporated and the residue was purified by
TLC (hexane:EtOAc=4:1). The ee values were determined by GLC with
a Chrompack CP-Cyclodextrin-B-236-M-19 column (0.25mm i.d. x
50m) and HPLC with a Chiralcel OD column. The absolute
configuration of alcohols was determined by the comparison of the
13
1H); C NMR (CDCl ) δ: 19.23, 29.28, 29.34, 34.84, 65.00,
3
65.57, 73.83 99.54, 117.18, 118.49, 126.38, 127.51, 128.10,
129.16, 129.61, 137.39, 138.62, 160.70, 166.03; MS m/z (rel
+
intensity): 367 (M , 12); Anal. Calcd. for C
H NO : C, 75.17;
23 29 3
H, 7.95; N, 3.81. Found: C, 74.76; H, 8.06; N, 3.74.
13
optical rotation of literature data.
(11) a) Casiraghi, G.; Casnati, G.; Puglia, G.; Sartori, G.; Terenghi, G.
J. Chem. Soc. Perkin Trans. 1, 1980, 862. b) Hayashi, M.;
Miyamoto, Y.; Inoue, T.; Oguni, N. J. Org. Chem. 1993, 58, 1515.
References and Notes
25
25
(12) 6a. [α]
-39.58 (c 1.0, CHCl ); 6b. [α]
-21.48 (c 1.0,
D
3
D
25
25
(1) New address: Department of Materials Technology, Faculty of
Engineering, Chiba University, Inage, Chiba 263-8522 Japan.
Fax : 81-43-290-3401; e-mail : tmino@planet.tc.chiba-u.ac.jp
CHCl ); 6c. [α]
-36.78 (c 1.0, CHCl ); 6d. [α]
-34.98 (c
25
3
D
3
D
25
1.0, CHCl ); 6e. [α]
-31.18 (c 1.0, CHCl ); 6f. [α]
D
-30.48
3
D
3
(c 1.0, CHCl ).
3
(2) Seyden-Penne, J. in Chiral Auxiliaries and Ligands in Asymmetric
Synthesis; John Wiley & Sons, Inc., New York, 1995.
(13) Soai, K.; Ookawa, A.; Kaba, T.; Ogawa, K. J. Am. Chem. Soc.
1987, 109, 7111.