LETTER
Chem. Soc. 1994, 116, 1597. (b) Holton, R. A.; Kim, H. B.;
Selective Acylation Reactions of an Isotaxane Tetraol
1549
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4: colorless oil; [a] D-32.6 (c 0.05, CHCl3); IR (film, cm )
3504 (br), 1713, 1514, 1451, 1271, 1098; 1H NMR (300 MHz,
CDCl3): d = 7.96 (d, J = 7.1 Hz, 2 H), 7.62 (d, J = 7.1 Hz, 2
H), 7.56 (t, J = 7.4 Hz, 1 H), 7.43-7.28 (m, 8 H), 7.23-7.10 (m,
4 H), 6.78 (d, J = 8.6 Hz, 2 H), 5.27-5.25 (m, 1 H), 4.86 (d, J
= 7.6 Hz, 1 H), 4.80-4.57 (m, 4 H), 4.56 (d, J = 7.7 Hz, 2 H),
4.49 (t, J = 3.2 Hz, 2 H), 4.45 (s, 1 H), 4.33 (d, J = 7.2 Hz, 1
H), 4.14 (dd, J = 11.0, 3.3 Hz, 1 H), 3.78 (s, 3 H), 3.68 (s, 1
H), 3.58 (dd, J = 12.6, 4.0 Hz, 1 H), 3.33 (s, 3 H), 2.96-2.27
(series of m, 5 H), 2.05-1.54 (series of m, 6 H), 1.30 (s, 3 H),
1.11 (s, 3 H), 1.06 (s, 3 H). 13C NMR (75 MHz, CDCl3): d =
210.5, 166.7, 164.7, 159.1, 137.5, 133.1, 132.8, 130.3, 129.9,
129.6 (2 C), 129.5, 129.4 (2 C), 129.1 (2 C), 128.5 (2 C), 128.1
(2 C), 127.9 (2 C), 127.8, 113.7 (2 C), 95.3, 94.2, 84.7, 83.4,
81.1, 80.6, 75.9, 74.2, 72.5, 69.8, 64.1, 58.3, 56.6, 55.7, 55.2,
49.6, 39.4, 32.4, 31.7, 31.1, 28.3, 26.6, 17.2, 11.7. MS (FAB)
(M+) calcd 880.40, obsd 880.41.
Somoza, C.; Liang, F.; Biediger, R. J.; Boatman, P. D.;
Shindo, M.; Smith, C. C.; Kim, S.; Nadizadeh, H.; Suzuki, Y.;
Tao, C.; Vu, P.; Tang, S.; Zhang, P.; Murthi, K. K.; Gentile, L.
N.; Liu, J. H. J. Am. Chem. Soc. 1994, 116, 1599.
(4) (a) Nicolaou, K. C.; Nantermet, P. G.; Ueno, H.; Guy, R. K.;
Couladouros, E. A.; Sorensen, E. J. J. Am. Chem. Soc. 1995,
117, 624. (b) Nicolaou, K. C.; Liu, J.-J.; Yang, Z.; Ueno, H.;
Sorensen, E. J.; Claiborne, C. F.; Guy, R. K.; Hwang, C.-K.;
Nakada, M.; Nantermet, P. G. J. Am. Chem. Soc. 1995, 117,
634. (c) Nicolaou, K. C.; Yang, Z.; Liu, J.-J.; Nantermet, P.
G.; Claiborne, C. F.; Renaud, J.; Guy, R. K.; Shibayama, K. J.
Am. Chem. Soc. 1995, 117, 645. (d) Nicolaou, K. C.; Ueno, H.;
Liu, J.-J.; Nantermet, P. G.; Yang, Z.; Renaud, J.; Paulvannan,
K.; Chadha, R. J. Am. Chem. Soc. 1995, 117, 653.
(5) Danishefsky, S. J.; Masters, J. J.; Young, W. B.; Link, J. T.;
Snyder, L. B.; Magee, T. V.; Jung, D. K.; Isaacs, R. C. A.;
Bornmann, W. G.; Alaimo, C. A.; Coburn, C. A.; Di Grandi,
M. J. J. Am. Chem. Soc. 1996, 118, 2843.
(6) (a) Wender, P. A.; Badham, N. F.; Conway, S. P.; Floreancig,
P. E.; Glass, T. E.; Gränicher, C.; Houze, J. B.; Jänichen, J.;
Lee, D.; Marquess, D. G.; McGrane, P. L.; Meng, W.;
Mucciaro, T. P.; Mühlebach, M.; Natchus, M. G.; Paulsen, H.;
Rawlins, D. B.; Satkofsky, J.; Shuker, A. J.; Sutton, J. C.;
Taylor, R. E.; Tomooka, K. J. Am. Chem. Soc. 1997, 119,
2755. (b) Wender, P. A.; Badham, N. F.; Conway, S. P.;
Floreancig, P. E.; Glass, T. E.; Houze, J. B.; Krauss, N. E.;
Lee, D.; Marquess, D. G.; McGrane, P. L.; Meng, W.;
Natchus, M. G.; Shuker, A. J.; Sutton, J. C.; Taylor, R. E. J.
Am. Chem. Soc. 1997, 119, 2757.
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5: colorless oil; [a] D+15.0 (c 0.03, CHCl3); IR (film, cm )
3403, 1720, 1287, 1110, 1037; 1H NMR (300 MHz, CDCl3):
d = 8.05 (d, J = 7.5 Hz, 2 H), 7.81 (d, J = 7.6 Hz, 2 H), 7.59 (d,
J = 7.6 Hz, 2 H), 7.54 (d, J = 7.5 Hz, 1 H), 7.42-7.18 (m, 11
H), 7.12 (d, J = 8.4 Hz, 2 H), 6.98 (t, J = 7.7 Hz, 2 H), 6.72 (d,
J = 8.4 Hz, 2 H), 5.31 (d, J = 11.3 Hz, 1 H), 4.95 (d, J = 11.9
Hz, 1 H), 4.88 (d, J = 7.6 Hz, 1 H), 4.76-4.71 (m, 3 H), 4.58
(d, J = 10.7 Hz, 1 H), 4.50-4.28 (m, 5 H), 4.07 (dd, J = 11.3,
3.1 Hz, 1 H), 3.76 (s, 3 H), 3.60-3.56 (m, 2 H), 3.37 (s, 3 H),
3.32 (t, J = 13.0 Hz, 1 H), 2.82 (d, J = 13.1 Hz, 1 H), 2.68 (s,
2 H), 2.63 (d, J = 12.8 Hz, 1 H), 2.22-1.79 (m, 4 H), 1.45 (s, 3
H), 1.28 (s, 3 H), 1.25 (s, 3 H), 1.21-0.86 (m, 1 H). 13C NMR
(75 MHz, CDCl3): d = 209.5, 166.1, 164.3, 159.0, 137.5,
132.8, 132.6, 132.5, 130.9, 130.0, 129.8, 129.6 (2 C), 129.4 (2
C), 129.1 (2 C), 128.4 (2 C), 128.3 (2 C), 128.1 (2 C), 127.9
(2 C), 127.74, 127.70, 113.6 (2 C), 95.3, 93.9, 89.9, 84.3, 81.7,
80.1, 75.5, 72.1, 69.7, 69.3, 63.1, 57.5, 55.7, 55.1, 55.0, 51.7,
40.1, 31.3, 30.8, 29.8, 29.6, 28.0, 17.8, 11.5. MS (FAB) (M+)
calcd 984.43, obsd 984.51.
(7) Mukaiyama, T.; Shiina, I.; Iwadare, H.; Sakoh, H.; Tani, Y.;
Hasegawa, M.; Saitoh, K. Proc. Japan Acad., Ser. B 1997, 73,
95.
(8) Morihira, K.; Hara, R.; Kawahara, S.; Nishimori, T.;
Nakamura, N.; Kusama, H.; Kuwajima, I. J. Am. Chem. Soc.
1998, 120, 12980.
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(9) Paquette, L. A.; Montgomery, F. J.; Wang, T.-Z. J. Org.
Chem. 1995, 60, 7857.
6: colorless oil; [a] D+17.9 (c 0.07, CHCl3); IR (film, cm )
1721, 1286, 1249, 1098, 1037; 1H NMR (300 MHz, CDCl3):
d = 8.03 (d, J = 7.1 Hz, 2 H), 7.61 (d, J = 7.1 Hz, 2 H), 7.52-
7.45 (m, 2 H), 7.41-7.34 (m, 2 H), 7.33-7.26 (m, 5 H), 7.24 (d,
J = 8.6 Hz, 2 H), 6.99 (t, J = 7.9 Hz, 2 H), 6.85 (d, J = 8.6 Hz,
2 H), 5.28 (dd, J = 12.3, 1.7 Hz, 1 H), 4.78 (d, J = 7.6 Hz, 1
H), 4.71-4.57 (m, 3 H), 4.53 (d, J = 1.4 Hz, 2 H), 4.45-4.36 (m,
3 H), 4.20 (d, J = 8.7 Hz, 1 H), 3.97-3.91 (m, 2 H), 3.79 (s, 3
H), 3.57 (dd, J = 12.3, 3.9 Hz, 1 H), 3.35 (s, 3 H), 3.24 (d, J =
13.7 Hz, 1 H), 2.72-2.65 (m, 3 H), 2.47 (d, J = 11.4 Hz, 1 H),
2.19-2.14 (m, 1 H), 2.00-1.97 (m, 1 H), 1.79 (s, 3 H), 1.77-
1.70 (m, 1 H), 1.46 (s, 3 H), 1.45-1.41 (m, 2 H), 1.32 (s, 3 H),
1.27 (s, 3 H), 1.23 (s, 3 H). 13C NMR (75 MHz, CDCl3): d =
209.4, 165.5, 164.5, 159.1, 137.6, 133.6, 132.6, 132.4, 131.2,
130.2, 129.7 (2 C), 129.6 (2 C), 129.3 (2 C), 128.45, 128.42 (2
C), 128.3, 127.9 (2 C), 127.7 (2 C), 113.7 (2 C), 109.4, 95.2,
93.9, 89.9, 86.9, 81.3, 80.3, 80.1, 71.8, 69.6, 69.4, 64.2, 57.9,
55.7, 55.2, 54.8, 51.7, 39.2, 31.9, 31.3, 29.8, 29.2, 28.2, 26.8,
26.7, 17.7, 10.5. MS (FAB) (M+) calcd 920.43, obsd 920.46.
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(10) 2: colorless oil; [a] D-32.6 (c 0.05, CHCl3); IR (film, cm )
3393 (br), 1702, 1611, 1514, 1466; 1H NMR (300 MHz,
CDCl3): d = 7.33 (br s, 5 H), 7.18 (d, J = 8.4 Hz, 2 H), 6.87 (d,
J = 8.5 Hz, 2 H), 4.83 (d, J = 7.6 Hz, 1 H), 4.74 (d, J = 7.5 Hz,
1 H), 4.69 (d, J = 11.7 Hz, 1 H), 4.53-4.45 (m, 4 H), 4.37 (d, J
= 10.5 Hz, 1 H), 4.26 (d, J = 7.1 Hz, 1 H), 4.15-4.10 (m, 2 H),
4.04 (d, J = 11.6 Hz, 1 H), 3.79 (s, 3 H), 3.54-3.33 (m, 4 H),
3.30 (s, 3 H), 2.82-2.57 (m, 4 H), 2.32-2.30 (m, 1 H), 1.92-
1.70 (m, 5 H), 1.27-1.17 (m, 2 H), 1.15 (s, 3 H), 1.00 (s, 3 H),
0.96 (s, 3 H). 13C NMR (75 MHz, CDCl3): d = 210.7, 159.6,
137.5, 129.4 (2 C), 129.2, 128.5 (2 C), 127.9, 127.8 (2 C),
114.1 (2 C), 95.3, 94.4, 86.8, 85.4, 81.1, 80.1, 74.8, 74.1, 72.4,
69.8, 61.0, 58.6, 57.1, 55.6, 55.3, 47.1, 36.3, 33.3, 32.6, 31.9,
28.7, 25.9, 17.1, 12.4. MS (FAB) (M+) calcd 672.35, obsd
672.60.
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3: colorless oil; [a] D-31.9 (c 0.16, CHCl3); IR (film, cm )
3396 (br), 1713, 1514, 1271; 1H NMR (300 MHz, CDCl3): d
= 7.93 (d, J = 7.7 Hz, 2 H), 7.53-7.29 (m, 8 H), 7.15 (d, J = 8.6
Hz, 2 H), 6.76 (d, J = 8.5 Hz, 2 H), 4.84 (d, J = 7.7 Hz, 1 H),
4.78-4.66 (m, 3 H), 4.58-4.42 (m, 7 H), 4.28 (d, J = 7.2 Hz, 1
H), 4.21 (dd, J = 11.3, 4.0 Hz, 1 H), 3.77 (s, 3 H), 3.65 (s, 1
H), 3.52 (dd, J = 12.3, 4.1 Hz, 1 H), 3.31 (s, 3 H), 2.82-2.67
(m, 4 H), 2.50-2.20 (m, 2 H), 2.04 (s, 1 H), 1.87-1.67 (m, 5 H),
1.15 (s, 3 H), 1.13 (s, 3 H), 1.02 (s, 3 H). 13C NMR (75 MHz,
CDCl3): d = 210.9, 166.3, 159.2, 137.4, 133.0, 130.1, 129.9,
129.6 (2 C), 129.3, 129.2 (2 C), 128.5 (2 C), 128.3 (2 C), 127.8
(2 C), 113.7 (2 C), 95.1, 94.5, 87.1, 83.3, 81.1, 80.3, 74.9,
74.7, 72.1, 69.7, 63.2, 59.0, 57.2, 55.6, 55.2, 47.3, 37.6, 33.2,
32.4, 31.8, 28.3, 25.9, 17.0, 12.2.
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7: colorless oil; [a] D-24.8 (c 0.6, CHCl3); IR (film, cm )
1719, 1286, 1111; 1H NMR (300 MHz, CDCl3): d = 8.03 (d, J
= 8.2 Hz, 2 H), 7.89 (d, J = 8.2 Hz, 2H), 7.55-7.49 (m, 4 H),
7.49-7.21 (m, 8 H), 7.20 (d, J = 8.2 Hz, 2 H), 7.02-6.90 (m, 4
H), 6.82 (d, J = 8.1 Hz, 2 H), 5.31-5.15 (m, 3 H), 4.89 (d, J =
7.7 Hz, 1 H), 4.76-4.69 (m, 3 H), 4.56-4.36 (m, 6 H), 4.06-4.01
(m, 1 H), 3.87-3.67 (m, 3 H), 3.79 (s, 3 H), 3.57-3.48 (m, 1 H),
3.37 (s, 3 H), 2.87-2.82 (m, 1 H), 2.69-2.58 (m, 3 H), 2.27-
2.00 (m, 3H), 1.78-1.61 (m, 1 H), 1.48 (s, 3 H), 1.43 (s, 1 H),
1.27 (s, 3 H), 1.25 s, 3H), 0.99-0.83 (m, 3 H), -0.04 (s, 9 H).
13C NMR (75 MHz, CDCl3): d = 209.7, 166.3, 165.7, 164.1,
159.1, 137.5, 132.6, 132.4, 132.3, 131.2, 129.95, 129.92,
Synlett 1999, No. 10, 1547–1550 ISSN 0936-5214 © Thieme Stuttgart · New York