3004
N. Ogawa, Y. Kobayashi / Tetrahedron Letters 52 (2011) 3001–3004
Prostaglandins Leukot. Essent. Fatty Acids 2008, 79, 157–163; (e) Hassan, I. R.;
Gronert, K. J. Immunol. 2009, 182, 3223–3232.
5.98 (d, J = 15 Hz, 1 H), 6.51 (dd, J = 15, 7 Hz, 1 H), 7.35–7.51 (m, 6 H), 7.62–7.77
(m, 4 H); 13C NMR (75 MHz, CDCl3) d 19.3 (ꢀ), 27.0 (+), 39.1 (ꢀ), 59.1 (ꢀ), 74.4
(+), 77.7 (+), 127.7 (+), 127.8 (+), 129.9 (+), 130.0 (+), 133.1 (ꢀ), 133.3 (ꢀ), 135.8
2. Ogawa, N.; Kobayashi, Y. Tetrahedron Lett. 2009, 50, 6079–6082.
3. (a) Serhan, C. N.; Gotlinger, K.; Hong, S.; Lu, Y.; Siegelman, J.; Baer, T.; Yang, R.;
Colgan, S. P.; Petasis, N. A. J. Immunol. 2006, 1848–1859; (b) Hong, S.; Gronert,
K.; Devchand, P. R.; Moussignac, R.-L.; Serhan, C. N. J. Biol. Chem. 2003, 278,
14677–14687.
4. Serhan, C. N.; Yang, R.; Martinod, K.; Kasuga, K.; Pillai, P. S.; Porter, T. F.; Oh, S.
F.; Spite, M. J. Exp. Med. 2009, 206, 15–23.
5. (a) Shimazaki, T.; Kobayashi, Y.; Sato, F. Chem. Lett. 1988, 1785–1788; (b)
Kobayashi, Y.; Shimazaki, T.; Taguchi, H.; Sato, F. J. Org. Chem. 1990, 55, 5324–
5335.
(+), 136.0 (+), 147.4 (+). Alcohol 21: ½a D24
ꢁ
+11 (c 0.94, CHCl3); 1H NMR (300 MHz,
CDCl3) d 1.07 (s, 9 H), 1.48–1.72 (m, 2 H), 2.09 (q, J = 7 Hz, 1 H), 2.16–2.30 (m, 1
H), 2.62 (t, J = 7 Hz, 1 H), 3.63 (t, J = 6.5 Hz, 2 H), 4.06–4.16 (m, 1 H), 5.20–5.52
(m, 4 H), 5.97 (dd, J = 14, 1 Hz, 1 H), 6.47 (dd, J = 14, 6.5 Hz, 1 H), 7.32–7.47 (m,
3 H), 7.57–7.75 (m, 2 H); 13C NMR (75 MHz, CDCl3) d 23.6 (ꢀ), 25.7 (ꢀ), 27.0 (+),
29.8 (ꢀ), 32.5 (ꢀ), 35.3 (ꢀ), 62.6 (ꢀ), 75.7 (+), 124.3 (+), 127.67 (+), 127.69 (+),
128.4 (+), 129.5 (+), 129.9 (+), 130.6 (+), 135.9 (+), 136.0 (+), 147.8 (+). Iodide
4b: ½a 2D3
ꢁ
+15 (c 0.66, CHCl3); 1H NMR (300 MHz, CDCl3) d 2.26–2.42 (m, 6 H),
2.70–2.92 (m, 2 H), 3.67 (s, 3 H), 4.15 (q, J = 6 Hz, 1 H), 5.31–5.48 (m, 3 H), 5.52–
5.64 (m, 1 H), 6.38 (dd, J = 14.5, 1.5 Hz, 1 H), 6.60 (dd, J = 14.5, 6 Hz, 1 H); 13C
NMR (75 MHz, CDCl3) d 22.9 (ꢀ), 25.9 (ꢀ), 34.0 (ꢀ), 34.8 (ꢀ), 51.7 (+), 73.9 (+),
77.4 (+), 124.2 (+), 128.2 (+), 129.0 (+), 131.9 (+), 147.8 (+), 173.8 (ꢀ). Acetylene
6. (a) Caruso, T.; Spinella, A. Tetrahedron 2003, 59, 7787–7790; (b) Tallman, K. A.;
Rector, C. L.; Porter, N. A. J. Am. Chem. Soc. 2009, 131, 5635–5641.
7. Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J.
Am. Chem. Soc. 1981, 103, 6237–6240.
29: ½a 2D3
ꢁ
+15 (c 0.94, CHCl3); 1H NMR (300 MHz, CDCl3) d 0.05 (s, 3 H), 0.08 (s, 3
8. Prepared by PCC oxidation of the corresponding alcohol i, which was used for
H), 0.88 (s, 9 H), 0.96 (t, J = 7.5 Hz, 3 H), 1.90–2.14 (m, 2 H), 2.15–2.37 (m, 2 H),
3.08–3.13 (m, 1 H), 4.59–4.74 (m, 1 H), 5.31–5.58 (m, 3 H), 5.88–6.01 (m, 1 H);
13C NMR (75 MHz, CDCl3) d ꢀ4.8 (+), ꢀ4.4 (+), 14.3 (+), 20.8 (ꢀ), 25.9 (+), 35.5
the synthesis of RvE1.2
PCC (1.4 equiv)
I
Celite (220 wt % of PCC)
(ꢀ), 70.9 (+), 79.9 (ꢀ), 82.4 (ꢀ), 107.3 (+), 124.3 (+), 133.8 (+), 148.6 (+). PD1
OH
OTBDPS
3a
(1): UV (MeOH) kmax 270 with shoulders 261 (s), 281 (s) nm (lit.
271 with
19
shoulders 262 (s), 282 (s) nm); 1H NMR (500 MHz, CDCl3) d 0.97 (t, J = 7.5 Hz, 3
H), 1.92–2.12 (m, 2 H), 2.20–2.50 (m, 8 H), 2.70–2.82 (m, 1 H), 2.84–2.95 (m, 1
H), 4.16–4.28 (m, 1 H), 4.54–5.64 (m, 1 H), 5.22–5.48 (m, 5 H), 5.50–5.61 (m, 2
H), 5.70–5.83 (m, 1 H), 6.10 (dt, J = 4.5, 11 Hz, 1 H), 6.14–6.36 (m, 2 H), 6.52 (dd,
J = 14.5, 11 Hz, 1 H); 1H NMR (500 MHz, CD3OD) d 0.93 (t, J = 7.5 Hz, 3 H), 1.95–
2.10 (m, 2 H), 2.10–2.42 (m, 8 H), 2.76–2.90 (m, 2 H), 4.02–4.18 (m, 1 H), 4.50–
5.60 (m, 1 H), 5.29–5.57 (m, 6 H), 5.64–5.78 (m, 2 H), 6.07 (dd, J = 11, 11 Hz, 1
H), 6.18–6.34 (m, 2 H), 6.50 (dd, J = 13, 11.5 Hz, 1 H); 13C NMR (75 MHz, CDCl3)
d 14.3, 18.5, 23.9, 26.0, 29.2, 29.8, 35.4, 67.8, 71.8, 123.6, 124.9, 128.2, 128.9,
129.2, 130.3, 130.5, 131.5, 133.3, 133.9, 135.5, 136.8, 175.6; 13C NMR (75 MHz,
CD3OD) d 13.6, 20.7, 23.0, 25.7, 29.8, 34.3, 35.4, 67.5, 72.0, 124.3, 125.5, 128.3,
129.0, 129.1, 129.6, 130.0, 130.4, 133.7, 133.8, 134.0, 137.0, 176.5; HR-MS
(FAB) calcd for C22H31O4 [(M–H)+] 359.2222, found 359.2222.
CH2Cl2, 1 h, 100%
i
9. (a) Gao, Y.; Klunder, J. M.; Hanson, R. M.; Ko, S. Y.; Masamune, H.; Sharpless, K.
B. J. Am. Chem. Soc. 1987, 109, 5765–5780; (b) Kitano, Y.; Matsumoto, T.; Sato, F.
Tetrahedron 1988, 44, 4073–4086.
10. Epoxide 24 can be converted to the cis bromo olefin 25 according to the
established procedure.11 However, 24 was not used in the present synthesis of
PD1 simply due to completion of the synthesis with 25 derived from (S)-23.
11. Okamoto, S.; Shimazaki, T.; Kobayashi, Y.; Sato, F. Tetrahedron Lett. 1987, 28,
2033–2036.
12. Alcohol i (precursor of 19): ½a D23
ꢁ
+66 (c 0.632, CHCl3); 1H NMR (300 MHz, CDCl3)
d 1.10 (s, 9 H), 1.05–2.04 (m, 2 H), 3.56–3.78 (m, 2 H), 4.35 (q, J = 6 Hz, 1 H),