988
LETTERS
SYNLETT
-1
1
cm ; H NMR (CDCl , 300 MHz): δ (ppm) 7.50 - 7.12 (m, 9H),
3
6.45 - 6.29 (m, 2H), 4.16 (d, J = 14 Hz, 1H), 3.94 (d, J = 14 Hz,
1H), 3.67 (d, J = 6.6 Hz, 2H), 3.31 - 3.11 (m, 6H), 3.24 (s, 6H),
13
2.15 - 1.88 (m, 2H), 1.73 - 1.58 (m, 2H); C NMR (CDCl ): δ
3
77
74.4, 60.6, 58.9, 53.7, 29.2, 27.2 ppm; Se NMR (CDCl ): δ
3
299.8 ppm; Anal Calcd for C
H O NSe: C, 64.85; H, 7.03; N,
24 31 2
3.15 %. Found: C, 64.93; H, 7.04; N, 2.99 %. 1c: yellow oil;
Scheme 3
31
[α]
-4.58° (c 0.978, CHCl ); IR (neat): 3420, 2974, 1669,
3
D
-1
1
1586, 1450, 750 cm ; H NMR (CDCl , 300 MHz): δ (ppm) 7.44
3
- 7.08 (m, 9H), 6.29 - 6.15 (m, 2H), 5.50 - 5.42 (brs, 2H), 3.80 (d,
J = 13 Hz, 1H), 3.66 - 3.58 (m, 3H), 3.08 - 3.01 (m, 1H), 2.92 -
In conclusion, we achieved the asymmetric [2,3]sigmatropic
rearrangement of optically active allylic selenides 1 to afford the
2.84 (m, 1H), 2.32 - 2.06 (m, 2H), 1.90 - 1.79 (m, 1H), 1.72 - 1.54
…
13
corresponding chiral allylic alcohol 3. The intramolecular Se
N
(m, 2H); C NMR (CDCl ): δ 177.0, 66.7, 59.8, 53.1, 29.6, 29.0,
3
77
interaction is not only responsible for the asymmetric induction but also
22.8 ppm; Se NMR (CDCl ): δ 291.6 ppm; HRMS Found: m/z
3
the suppression of racemization of the chiral intermediate selenoxide 2.
400.1000; Calcd for C
H N OSe: M, 400.1053. 1d: yellow oil;
21 24 2
31
[α]
-44.5° (c 0.676, CHCl ); IR (neat): 2952, 1734, 1437,
3
D
-1
1
1201, 1174, 752 cm ; H NMR (CDCl , 300 MHz): δ (ppm) 7.52
References and Notes
3
- 7.14 (m, 9H), 6.36 - 6.31 (m, 2H), 3.93 (d, J = 13 Hz, 1H), 3.84
(d, J = 13 Hz, 1H), 3.70 - 3.64 (m, 2H), 3.61 (s, 3H), 3.43 - 3.36
(1) (a) Liotta, D. Organoselenium Chemistry; Wiley: London, 1987.
(b) Paulmier, C. Selenium Reagents and Intermediates in Organic
Synthesis; Pergamon Press, Oxford: New York, 1986. (c)
Nicolaou, K. C.; Petasis, N. A. Selenium in Natural Products
Synthesis; CIS Inc.: Philadelphia PA, 1984.
(m, 1H), 2.99 - 2.90 (m, 1H), 2.55 - 2.45 (m, 1H), 2.16 - 2.01 (m,
13
1H), 1.99 - 1.66 (m, 3H); C NMR (CDCl ): δ 174.7, 64.4, 57.8,
3
77
52.1, 51.3, 29.7, 29.2, 23.1 ppm; Se NMR (CDCl ): δ 298.6
3
ppm; HRMS Found: m/z 415.1064; Calcd for C
H NO Se: M,
22 25 2
(2) For reviews: (a) Kamigata, N.; Shimizu, T. In Reviews on
Heteroatom Chemistry; Oae, S., Ed.; MYU: Tokyo, 1991; Vol. 4,
p226. (b) Tomoda, S.; Usuki, Y.; Fujita, K.; Iwaoka, M. In
Reviews on Heteroatom Chemistry; Oae, S., Ed.; MYU: Tokyo,
1991; Vol. 4, p249. (c) Fujita, K. J. Syn. Org. Chem., Jpn. 1996,
54, 166. (d) Fujita, K. In Reviews on Heteroatom Chemistry; Oae,
S., Ed.; MYU: Tokyo, 1997; Vol. 16, p101.
31
415.1049. 1e: white powder; [α]
-8.02° (c 1.03, CHCl ); IR
3
D
-1
1
(KBr): 2928, 2874, 2812, 1462, 1448, 1114, 961, 750 cm ;
H
NMR (CDCl , 300 MHz): δ (ppm) 7.51 - 7.13 (m, 9H), 6.36 - 6.31
3
(m, 2H), 4.14 (d, J = 13 Hz, 1H), 3.70 - 3.64 (m, 2H), 3.56 (d, J =
13 Hz, 1H), 3.52 - 3.44 (m, 1H), 3.30 (s, 3H), 3.29 - 3.22 (m, 1H),
2.86 - 2.66 (m, 2H), 2.22 - 2.12 (m, 1H), 2.01 - 1.84 (m, 1H), 1.70
13
- 1.56 (m, 3H); C NMR (CDCl ): δ 76.1, 63.3, 59.9, 58.9, 54.1,
3
(3) (a) Tomoda, S.; Fujita, K.; Iwaoka, M. J. Chem. Soc., Chem.
Commun. 1990, 129. (b) Tomoda, S.; Fujita, K.; Iwaoka, M.
Phosphorus, Sulfur, and Silicon, and the Related Elements 1992,
67, 125. (c) Fujita, K.; Murata, K.; Iwaoka, M.; Tomoda, S.
Heteroatom Chem. 1995, 5, 247. (d) Fujita, K.; Iwaoka, M.;
Tomoda, S. Chem. Lett. 1994, 923. (e) Fujita, K.; Murata, K.;
Iwaoka, M.; Tomoda, S. Tetrahedron Lett. 1995, 36, 5219. (f)
Fujita, K.; Murata, K.; Iwaoka, M.; Tomoda, S. J. Chem. Soc.,
Chem. Commun. 1995, 1641. (g) Fujita, K.; Murata, K.; Iwaoka,
M.; Tomoda, S. Tetrahedron 1997, 53, 2029.
77
29.6, 28.7, 22.7 ppm; Se NMR (CDCl ): δ 297.2 ppm; HRMS
3
Found: m/z 401.1212; Calcd for C
H NOSe: M, 401.1256.
22 27
(7) Davis, F. A.; Stringer, O. D.; McCauley, J. P. Jr. Tetrahedron 1985,
41, 4747.
(8) Enomoto, M.; Shimizu, T.; Kamigata, N. the 74th Annual Meeting
of the Chemical Society of Japan, Kyoto, March, 1998, Abstract
3C202.
Shimizu, T.; Kobayashi, M.; Kamigata, N. Bull. Chem. Soc. Jpn.
1988, 61, 3761.
(4) (a) Iwaoka, M.; Tomoda, S. Phosphorus, Sulfur, and Silicon, and
the Related Elements 1992, 67, 125. (b) Iwaoka, M.; Tomoda, S. J.
Org. Chem. 1995, 60, 5299. (c) Iwaoka, M.; Tomoda, S. J. Am.
Chem. Soc. 1996, 118, 8077.
31
4: yellow oil; [α]
-23.5° (c 1.40, CHCl ); IR (neat): 2975,
3
D
-1
1
2926, 1444, 1116, 748 cm ; H NMR (CDCl , 300 MHz): δ
3
(ppm) 7.48 - 7.06 (m, 4H), 5.46 - 5.33 (m, 1H), 5.15 - 5.01 (m,
1H), 4.17 (d, J = 13 Hz, 1H), 3.61 (d, J = 13 Hz, 1H), 3.56 - 3.47
(m, 3H), 3.33 (s, 3H), 3.32 - 3.25 (m, 1H), 2.93 - 2.84 (m, 1H),
2.84 - 2.73 (m, 1H), 2.30 - 2.17 (m, 1H), 2.11 - 1.89 (m, 5H), 1.76
(5) For recent examples: (a) Reich, H. J.; Yelm, K. E. J. Org. Chem.
1991, 56, 5672. (b) Nishibayashi, Y.; Singh, J. D.; Fukuzawa, S.;
Uemura, S. J. Org. Chem. 1995, 60, 4114. (c) Kurose, N.;
13
- 1.63 (m, 3H), 1.72 (s, 3H), 1.68 (s, 3H), 1.59 (s, 3H); C NMR
Takahashi, T.; Koizumi, T. Tetrahedron 1997, 53, 12115.
(CDCl ): δ 76.1, 63.4, 59.6, 58.9, 54.2, 39.5, 28.6, 26.5, 26.4,
31
3
(6) 1a: pale yellow powder; [α]
+99.3° (c 1.44, CHCl ); IR (KBr):
3
D
77
25.5, 22.7, 17.5, 15.6 ppm; Se NMR (CDCl ): δ 279.4 ppm;
-1
1
3
3034, 2906, 2854, 1456, 1388, 1125, 756 cm ; H NMR (CDCl ,
3
HRMS Found: m/z 421.1924; Calcd for C
H NOSe: M,
23 35
300 MHz): δ (ppm) 7.68 - 7.11 (m, 19H), 6.40 - 6.25 (m, 2H),
5.47 (s, 2H), 4.77 (d, J = 16 Hz, 1H), 4.37 (d, J = 2.1 Hz, 2H), 4.08
(d, J = 13 Hz, 2H), 3.92 (d, J = 16 Hz, 1H), 3.86 (dd, J = 13, 2.4
421.1882.
1
(11) We determined the e.e. of 5 by integration of H NMR absorptions
due to -C(OH)CH by adding Eu(tfc) . The absolute configuration
13
Hz, 2H), 3.70 (d, J = 6.3 Hz, 2H), 3.48 (s, 2H); C NMR
3
3
77
of the major enantiomer of 5 was determined by comparison with
(CDCl ): δ 99.7, 79.5, 66.8, 58.3, 53.8, 29.9 ppm; Se NMR
3
31
1
(CDCl ): δ 290.2 ppm. 1b: yellow oil; [α]
+43° (c 0.33,
the commercially available (R)-linalool by chemical shift of
NMR absorptions using Eu(tfc) .
H
3
D
CHCl ); IR (neat): 2922, 2874, 2828, 1460, 1450, 1114, 961, 748
3
3