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M. Asano et al.
LETTER
(17) Detailed discussions on this IMDA reaction will be
(5) Quite recently, three other synthetic studies of GKK1032s
and pyrrocidines were independently presented by
Kuwajima’s group, Tadano’s group, and Uchiro’s group:
(a) Arai, N.; Kuwajima, I. The 85th Annual Spring Meeting
of the Chemical Society of Japan, Yokohama Japan 2005,
Abstract 2, 872. (b) Kurosaka, J.; Sinkawa, T.; Miyazaki,
Y.; Munakata, R.; Takao, K.; Tadano, K. The 85th Annual
Spring Meeting of the Chemical Society of Japan, Yokohama
Japan 2005, Abstract 2, 874. (c) Hasegawa, D.; Sakuma,
Y.; Takagi, Y.; Uchiro, T. The 125th Annual Meeting of the
Pharmaceutical Society of Japan, Tokyo Japan 2005,
Abstract 4, 71.
(6) (a) Danishefsky, S.; Kitahara, T. J. Am. Chem. Soc. 1974, 96,
7807. (b) Danishefsky, S.; Kitahara, T.; Schuda, P. F. Org.
Synth., Coll. Vol. 7 1990, 312.
(7) (a) Izquierdo Cubero, I.; Portal Olea, M. D.; Garcia Poza, D.
Carbohydr. Res. 1985, 138, 135. (b) Schmid, C. R.; Bryant,
J. D.; Dowlatzedah, M.; Phillips, J. L.; Prather, D. E.;
Schantz, R. D.; Sear, N. L.; Vianco, C. S. J. Org. Chem.
1991, 56, 4056.
presented in a full account.
(18) The vinylstannane 9 was prepared from the known
compound i: (a) Scarlato, G. R.; DeMattei, J. A.; Chong, L.
S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org.
Chem. 1996, 61, 6139. (b) Baker, R.; Castro, J. L. J. Chem.
Soc., Perkin Trans. 1 1990, 47; via a two-step sequence of
reactions as shown in Scheme 6.
1) MnO2, CH2Cl2
Me
Me
r.t., 12 h
Bu3Sn
OH
Bu3Sn
2) CH3P+Ph3Br–, n-BuLi
THF, r.t., 2 h
i
9
( 51%, 2 steps )
Scheme 6
(19) Data for 7: Colorless viscous oil, [a]D20 +18.2 (c 0.23,
CHCl3). IR (neat): 607, 648, 731, 779, 897, 908, 985, 1043,
1097, 1167, 1194, 1240, 1273, 1373, 1435, 1655, 1722,
2860, 2933, 2947, 2979, 3463 cm–1. 1H NMR (500 MHz,
CDCl3): d = 1.31 (s, 3 H), 1.41–1.48 (m, 1 H), 1.50 (d,
J = 4.8 Hz, 1 H), 1.83–2.04 (m, 4 H), 1.87 (d, J = 1.0 Hz, 3
H), 1.92 (d, J = 1.0 Hz, 3 H), 2.06–2.19 (m, 3 H), 2.24–2.30
(m, 1 H), 2.61–2.76 (m, 2 H), 2.81–2.98 (m, 2 H), 3.74 (s, 3
H), 4.59–4.65 (m, 1 H), 5.03 (d, J = 10.7 Hz, 1 H), 5.17 (d,
J = 17.4 Hz, 1 H), 5.26 (br s, 1 H), 5.88 (br s, 1 H), 6.04 (dd,
J = 1.9, 15.6 Hz, 1 H), 6.37 (dd, J = 10.7, 17.4 Hz, 1 H), 6.94
(dd, J = 4.1, 15.6 Hz, 1 H). 13C NMR (125 MHz, CDCl3):
d = 13.3, 18.7, 21.0, 25.8, 26.0, 26.3, 32.0, 33.6, 34.6, 40.0,
44.5, 50.2, 51.7, 71.4, 112.2, 119.8, 133.1, 133.6, 137.7,
140.2, 142.0, 151.2, 166.8. HR-EIMS: m/z calcd for
C23H34O3S2 (M+): 422.1949; found: 422.1954.
(8) Data for 13: Pale yellow oil [a]D20 –55.7 (c 0.24, CHCl3). IR
(neat): 631, 733, 787, 852, 906, 920, 968, 1057, 1084, 1211,
1242, 1358, 1371, 1419, 1456, 1680, 1709, 1736, 2937, 2985
cm–1. 1H NMR (500 MHz, CDCl3): d = 1.30 (s, 3 H), 1.36 (s,
3 H), 1.38 (s, 3 H), 2.25 (s, 3 H), 2.49 (dd, J = 4.5, 17.1 Hz,
1 H), 2.60 (dd, J = 11.1, 17.1 Hz, 1 H), 2.71 (ddd, J = 2.7,
4.5, 11.1 Hz, 1 H), 3.36 (dd, J = 7.6, 8.2 Hz, 1 H), 4.01 (dd,
J = 6.7, 8.2 Hz, 1 H), 4.07–4.15 (m, 1 H), 6.07 (d, J = 10.2
Hz, 1 H), 6.66 (d, J = 10.2 Hz, 1 H). 13C NMR (125 MHz,
CDCl3): d = 17.6, 25.0, 25.8, 26.2, 34.3, 40.1, 53.4, 67.6,
74.3, 109.4, 129.0, 150.1, 198.0, 208.1. HR-FABMS: m/z
calcd for C14H21O4 [(M + H)+]: 253.1440; found: 253.1448.
(9) Ortuño, R. M.; Ibarzo, J.; d’Angelo, J.; Dumas, F.; Alvarez-
Larena, A.; Piniella, J. F. Tetrahedron: Asymmetry 1996, 7,
127.
(10) Hendrickson, J. B.; Bergeron, R. Tetrahedron Lett. 1973, 14,
4607.
(11) (a) Corey, E. J.; Wollenberg, R. H. J. Am. Chem. Soc. 1974,
96, 5581. (b) Chen, S.-M. L.; Schaub, R. E.; Grudzinskas, C.
V. J. Org. Chem. 1978, 43, 3450.
(12) (a) Ichinose, Y.; Oda, H.; Oshima, K.; Utimoto, K. Bull.
Chem. Soc. Jpn. 1987, 60, 3468. (b) Smith, N. D.; Mancuso,
J.; Lautens, M. Chem. Rev. 2000, 100, 3257.
(20) Data for 6: White solid, mp 161–166 °C, [a]D20 +65.7 (c
0.45, CHCl3). IR (neat): 607, 621, 688, 783, 804, 852, 908,
995, 1047, 1159, 1223, 1259, 1331, 1375, 1435, 1716, 2875,
2931, 3500 cm–1. 1H NMR (500 MHz, CDCl3): d = 0.79 (s,
3 H), 1.28 (s, 3 H), 1.42–1.53 (m, 1 H), 1.69–1.83 (m, 3 H),
1.75 (s, 3 H), 1.89–2.00 (m, 3 H), 2.00–2.10 (m, 2 H), 2.11–
2.18 (m, 1 H), 2.33 (dt, J = 8.3, 12.0 Hz, 1 H), 2.52 (dt,
J = 13.4, 2.2 Hz, 1 H), 2.61 (d, J = 12.0 Hz, 1 H), 2.65–2.75
(m, 1 H), 2.77–2.87 (m, 2 H), 2.95–3.03 (m, 1 H), 3.68 (s, 3
H), 3.93–3.99 (m, 1 H), 4.85 (s, 1 H), 4.98 (dd, J = 1.5, 17.2
Hz, 1 H), 5.05, (dd, J = 1.5, 10.4 Hz, 1 H), 5.69 (dd, J = 10.4,
17.2 Hz, 1 H). 13C NMR (125 MHz, CDCl3): d = 13.3, 21.2,
25.9, 26.1, 26.4, 26.7, 34.5, 35.0, 35.3, 41.3, 42.4, 44.0, 50.3,
51.3, 52.3, 54.4, 55.5, 72.7, 114.5, 131.3, 135.4, 142.8,
174.8. HR-EIMS: m/z calcd for C23H34O3S2 (M+): 422.1949;
found 422.1950.
(13) Hart, D. W.; Blackburn, T. F.; Schwartz, J. J. Am. Chem.
Soc. 1975, 97, 679.
(14) Semmelhack, M. F.; Hooley, R. J. Tetrahedron Lett. 2003,
44, 5737.
(15) Gómez, A. M.; López, J. C.; Fraser-Reid, B. Synthesis 1993,
943.
(16) Han, X.; Stoltz, B. M.; Corey, E. J. J. Am. Chem. Soc. 1999,
121, 7600.
(21) In this IMDA reaction, a small amount (<10% yield) of
unidentified products was generated along with the desired
decahydrofluorene 6.
Synlett 2005, No. 10, 1539–1542 © Thieme Stuttgart · New York