2854
V. Krishna Reddy et al. / Tetrahedron Letters 45 (2004) 2851–2854
currently under progress and will be reported in our
future communications.
trated under vacuum. The resultant crude was purified on
silica gel column chromatography (20:1 chloroform–
methanol) to get pure epoxide 4a, colorless solid in 87%
1
yiled. Mp: 95–97 ꢁC. H NMR (CDCl
3
): d 1.62 (s, 3H,
3
CH ), 1.73–2.47 (m, 4H, H-4,5), 3.24 (d, 1H,
2
13
J
PH ¼ 25:8 Hz), 7.27–7.73 (m, 5H, Ph),
C NMR
), 22.76 (d, JCP ¼ 71:5 Hz, C-5),
Acknowledgements
(
2
CDCl ): d 19.25 (CH
8.48 (C-4), 34.61 (C-3), 57.77 (d, JCP ¼ 98:2 Hz, C-2),
3
3
3
V.K.R. greatly acknowledges the financial support from
the Satellite Venture Business Laboratory (SVBL),
Shizuoka University, Japan.
128.92 (d, JCP ¼ 11:36 Hz, C-3,5 of Ph), 130.03 (d,
2
J
CP ¼ 87:54, C-1 of Ph), 130.81 (d, JCP ¼ 9:36 Hz, C-2,6
4
31
of Ph), 132.82 (d, JCP ¼ 3:33 Hz, C-4 of Ph); P NMR
þ
(
CDCl
3
, H
3
PO
4
): d 49.92. MS (m=z): 209.18 (M +H) for
ꢀ1
C
11
H13PO
2
. IR (KBr): m (cm ) 2960 (C–H of epoxide),
1
270 and 828 (epoxide), 1194 (P@O).
1
0. Preparation of allylic alcohols (5a–g). Representative com-
pound 5a: To a )20 ꢁC suspension of trimethylsulfonium
iodide (1.2 g, 6.0 mmol, 6.1 equiv) in THF (10 mL) was
added n-BuLi (4.0 mL of 1.6 M hexane solution, 6.4 mmol,
References and notes
1
. For reviews, see: (a) Jacobsen, R. N. Acc. Chem. Res.
2
6
7
000, 33, 421–431; (b) Gorynski, S. J. Synthesis 1984, 629–
56; (c) Parker, R. E.; Isaacs, N. S. Chem. Rev. 1959, 737–
99; (d) Buchanan, J. G.; Sable, H. Z. In Selective Organic
Transformations; Thyagarajan, B. S., Ed.; John Wiley &
Sons: New York, 1964; Vol. 2, pp 1–523.
. (a) Alcaraz, L.; Harnett, J. J.; Mioskowski, C.; Martel, J.
P.; Le Gall, T.; Shin, D. S.; Falck, J. R. Tetrahedron Lett.
1994, 35, 5453–5456; (b) Alcaraz, L.; Cridland, A.;
Kinchin, E. Org. Lett. 2001, 3, 4051–4053.
. (a) Inouye, S.; Tsuruoka, T.; Niida, T. J. Antibiot. Ser. A.
1966, 19, 288; (b) Inouye, S.; Tsuruoka, T.; Ito, T.; Niida,
T. Tetrahedron 1968, 24, 2125.
. Nayak, U. G.; Whistler, R. L. J. Org. Chem. 1969, 34, 97.
. Yamashita, M.; Yamada, M.; Sugiura, M.; Nomoto, H.;
Oshikawa, T. Nippon Kagaku Kaishi 1987, 1207.
. Takayanagi, H.; Yamashita, M.; Seo, K.; Yoshida, H.;
Ogata, T.; Inokawa, S. Carbohydr. Res. 1974, 38, C19.
. (a) Yamamoto, H.; Hosoyamada, C.; Kawamoto, H.;
Inokawa, S.; Yamashita, M.; Armour, M. A.; Nakashima,
T. T. Carbohydr. Res. 1982, 102, 159; (b) Yamamoto, H.;
Hanaya, T.; Kawamoto, H.; Inokawa, S.; Yamashita, M.;
Nakashima, T. T. J. Org. Chem. 1985, 50, 3516.
. For recent reports, see: (a) Yamashita, M.; Krishna
Reddy, V.; Rao, L. N.; Haritha, B.; Maeda, M.; Suzuki,
K.; Totsuka, H.; Takahashi, M.; Oshikawa, T. Tetrahe-
dron Lett. 2003, 44, 2339; (b) Yamashita, M.; Krishna
Reddy, V.; Reddy, P. M.; Kato, Y.; Haritha, B.; Suzuki,
K.; Takahashi, M.; Oshikawa, T. Tetrahedron Lett. 2003,
6.5equiv). After 30–40min, epoxide 4a (0.2 g, 0.97 mmol,
1.0equiv) in THF (5 mL) was introduced and the reaction
slowly allowed to warm to 0 ꢁC over 1 h; the reaction
mixture was then stirred at ambient temperature for 2 h.
The reaction was quenched with water and extracted with
chloroform. The combined extracts were washed with brine,
dried over sodium sulfate, filtered, and concentrated. The
residues were purified on silica gel flash column chroma-
tography (20:1 chloroform–methanol) and recycle GPC
analysis to give pure allylic alcohol 5a as oily liquid.
2
3
1
1
1. To prepare sulfide derivatives, see: Krishna Reddy, V.;
Onogawa, J. I.; Rao, L. N.; Oshikawa, T.; Takahashi, M.;
Yamashita, M. J. Heterocycl. Chem. 2002, 39, 69–75.
2. All compounds (5a–g) were structurally characterized by
4
5
1
13
spectral H NMR (JEOL JNM-300 at 300.40 MHz),
C
6
31
NMR (JEOL JNM-300 at 75.0 MHz), P NMR (JEOL
JNM EX-90 at 36.18 MHz), mass (Kompact MALDI-
TOF MS).
7
J=10.5 Hz
J=17.1 Hz
Ph
8
Ha
P
C
J=1.5 Hz
O
Hb
OH
5
a
4
4, 3455; (c) Yamashita, M.; Reddy, P. M.; Kato, Y.;
Compound
methylphospholane 1-oxide): H NMR (CDCl
3H, CH ), 1.95–2.71 (m, 4H, H-4,5), 5.08–5.28 (dt, 2H,
5a
(1-phenyl-3-hydroxy-2-methylene-3-
1
Krishna Reddy, V.; Suzuki, K.; Oshikawa, T. Carbohydr.
Res. 2001, 336, 257; (d) Krishna Reddy, V.; Rao, L. N.;
Maeda, M.; Oshikawa, T.; Takahashi, M.; Yamashita, M.
Synth. Commun. 2002, 32, 69–74, and references cited
therein.
. Preparation of erythro-epoxides (4a–g). Representative
compound 4a (erythro-1-phenyl-2,3-epoxy-3-methylphos-
pholane 1-oxide): threo-Bromohydrin 3a (1.2 g, 4.2 mmol)
3
): 1.37 (s,
3
3
@CHH, JPH ¼ 10:5 & 17.1 Hz and JHH ¼ 1:5 Hz), 7.51–
1
3
7.76 (m, 5H, Ph), OH peak was not observed; C NMR
(CDCl ),
3
): d 23.86 (d, C-5, JCP ¼ 51:5 Hz), 28.12 (CH
3
9
33.57 (C-4), 72.19 (C-3), 112.62 (d, JCP ¼ 15:1 Hz, C-2),
3
128.54 (d,
J
CP ¼ 11:36 Hz, C-3,5 of Ph), 130.31 (d,
2
J
of Ph), 131.69 (d,
CP ¼ 87:54, C-1 of Ph), 130.76 (d, JCP ¼ 9:36 Hz, C-2,6
4
was treated with K
(
2
CO
20 mL) for 4 h at room temperature. The reaction mixture
3
(0.6 g, 4.5 mmol) in methanol
J
); P NMR (CDCl
CP ¼ 3:33 Hz, C-4 of Ph), 144.05
3
1
(@CH
2
3
, H
.
3 4
PO ): d 35.12. MS (m=z):
þ
was filtered, methanol was removed under vacuum and the
residue was dissolved in water (5 mL). The aqueous layer
was extracted with CHCl
extracts were dried over Na
222.12 (M ) for C12
H15PO
2
13. Yamashita, M.; Suzuki, K.; Kato, Y.; Iida, A.; Ikai, K.;
Reddy, P. M.; Oshikawa, T. J. Carbohydr. Chem. 1999, 18,
915–935.
3
(20 mL · 2), the combined
SO , filtered, and concen-
2
4