Lett., 1971, 1089; (c) S. Isoe, S. B. Hyeon, S. Katsumura and T.
Sakan, Tetrahedron Lett., 1972, 2517; (d) S. Isoe, S. Katsumura and
T. Sakan, Helv. Chim. Acta, 1973, 56, 1514.
7 (a) N. Furuichi, H. Hara, T. Osaki, H. Mori and S. Katsumura,
Angew. Chem., Int. Ed., 2002, 41, 1023; (b) N. Furuichi, H. Hara, T.
Osaki, M. Nakano, H. Mori and S. Katsumura, J. Org. Chem., 2004,
69, 7949.
8 A. Hoffmann-Roder and N. Krause, Angew. Chem., Int. Ed., 2004,
43, 1196.
9 K. Sonogashira, in Comprehensive Organic Synthesis, ed. B. M. Trost
and I. Fleming, Pergamon Press, Oxford, 1991, vol. 3, p. 521 and
references cited therein.
4.36 (d, 2H, J = 6.6 Hz), 2.36 (s, 3H), 1.92 (d, 3H, J = 1.2 Hz), 1.88
(d, 3H, J = 0.5 Hz); 13C NMR (100 MHz, CDCl3) d 199.7, 143.9,
139.6, 136.1, 135.6, 134.9, 123.8, 59.4, 25.5, 12.5, 11.6.
21 (a) J. B. Baudin, G. Hareau, S. A. Julia and O. Ruel, Tetrahedron
Lett., 1991, 32, 1175; (b) J. B. Baudin, G. Hareau, S. A. Julia and O.
Ruel, Bull. Soc. Chim. Fr., 1993, 130, 336; (c) J. B. Baudin, G. Hareau,
S. A. Julia, R. Lorne and O. Ruel, Bull. Soc. Chim. Fr., 1993, 130,
856; (d) P. R. Blakemore, W. J. Cole, P. J. Kocienski and A. Morley,
Synlett, 1998, 1, 26; (e) P. R. Blakemore, J. Chem. Soc., Perkin Trans.
1, 2002, 2563 and references cited therein.
22 The main pathway in the side-reactions would involve the [2,3]-
sigmatropic rearrangement of the intermediate sulfoxide to the
sulfenate ester, the details of which will be reported in a full account
of this work. See:D. A. Evans and G. C. Andrew, Acc. Chem. Res.,
1974, 7, 147.
10 A. Baumeler, W. Brade, A. Haag and C. H. Eugster, Helv. Chim.
Acta, 1990, 73, 700.
11 (a) H. Miyake and K. Yamamura, Chem. Lett., 1989, 981; (b) J.-F.
Betzer, F. Delalobe, B. Muller, A. Pancrazi and J. Prunet, J. Org.
Chem., 1997, 62, 7768 and references cited therein.
23 The thermal isomerization from cis to trans at the central C(15)–
C(15ꢀ) disubstituted double bond was also observed in our peridinin
synthesis.7 This feature was followed and detected by HPLC analysis,
the details of which will be reported in a full account of this work.
24 Conditions: column: Develosil 60-5 (4.6 × 250 mm); mobile phase:
THF–hexane–iPrOH = 15 : 67 : 3; flow rate: 1.0 ml min−1; UV-
detection: 450 nm; retention time: 22 min (all-E-isomer).
12 B. Domingues, B. Iglesias and A. R. de Lera, Tetrahedron, 1999, 55,
15071.
13 (a) I. Ahmed, R. N. Gedge and A. Nechwatel, J. Chem. Soc. C, 1968,
185; (b) G. Pattenden and B. C. L. Weedon, J. Chem. Soc. C, 1968,
1984.
14 Y. L. Behnani and M. F. Boehm, J. Org. Chem., 1995, 60, 1195.
15 Data for 3: [a]2D1 −23.47 (c 0.58, CHCl3); IR (KBr, cm−1) 3356, 2961,
2928, 2860, 1930, 1724, 1641, 1454, 1373, 1253, 1157, 1070; 1H NMR
(400 MHz, CD3OD) d 6.54 (dd, 1H, J = 15.1, 11.2 Hz), 6.27 (d, 1H,
J = 15.1 Hz), 6.07 (d, 1H, J = 10.5 Hz), 6.02 (s, 1H), 5.64 (t, 1H,
J = 6.8 Hz), 4.22 (d, 2H, J = 6.8 Hz), 4.20 (m, 1H), 2.18 (ddd, 1H,
J = 12.7, 3.9, 2.0 Hz), 1.89 (ddd, 1H, J = 14.9, 3.9, 2.0 Hz), 1.83 (s,
3H), 1.80 (s, 3H), 1.50–1.20 (m, 2H), 1.33 (s, 3H), 1.33 (s, 3H), 1.06
(s, 3H); 13C NMR (100 MHz, CD3OD) d 203.4, 137.7, 137.2, 133.1,
131.8, 128.9, 125.8, 118.4, 103.6, 73.1, 64.7, 59.5, 50.6, 50.1, 36.6,
32.9, 31.4, 29.6, 14.2, 12.6; EI+ HRMS found m/z 318.2193, calcd
for C20H30O3 M+ 318.2194.
25 Data for paracentrone (1): IR (KBr, cm−1) 3407, 2961, 2924, 2855,
1929, 1721, 1649, 1607, 1530, 1453, 1368, 1321, 1279, 1229, 1157,
1
1071, 1040, 992, 963; H NMR (400 MHz, CDCl3) d 7.14 (dq, 1H,
J = 10.5, 1.0 Hz), 6.73 (dd, 1H, J = 14.2, 11.5 Hz), 6.66 (d, 1H, J =
14.9 Hz), 6.63 (dd, 1H, J = 14.1, 11.5 Hz), 6.60 (dd, 1H, J = 14.6,
11.5 Hz), 6.59 (dd, 1H, J = 15.4, 10.7 Hz), 6.39 (d, 1H, J = 11.5 Hz),
6.34 (d, 1H, J = 15.1 Hz), 6.26 (d, 1H, J = 11.0 Hz), 6.12 (d, 1H,
J = 11.3 Hz), 6.03 (s, 1H), 4.32 (m, 1H), 2.36 (s, 3H), 2.27 (ddd, 1H,
J = 13.3, 4.2, 1.9 Hz), 1.991 (s, 3H), 1.985 (s, 3H), 1.96 (m, 1H), 1.94
(d, 3H, J = 1.0 Hz), 1.81 (s, 3H), 1.41 (m, 1H), 1.35 (s, 3H), 1.33
(s, 3H), 1.35 (m, 1H), 1.07 (s, 3H); 13C NMR (100 MHz, CDCl3) d
202.4, 199.4, 144.5, 139.9, 137.9, 137.0, 136.2, 135.5, 132.6, 132.3,
132.1, 129.4, 128.4, 125.6, 123.8, 117.7, 103.2, 73.0, 64.3, 49.5, 48.9,
35.8, 32.2, 31.4, 29.4, 25.6, 14.0, 12.9, 12.8, 11.7; ESI HRMS found
m/z 461.3065, calcd for C31H42O3 [M − H]− 461.3056.
16 D. B. Dess and J. C. Martin, J. Org. Chem., 1983, 48, 4156.
17 (a) B. H. Lipshutz, J. A. Kozlowski and R. S. Wilhelm, J. Org. Chem.,
1984, 49, 3943; (b) see also: ref. 11b.
18 P. A. Bieber, Ann. Chem., 1954, 9, 674.
26 M. Kuki, Y. Koyama and H. Nagae, J. Phys. Chem., 1991, 95, 7171.
27 (a) A. Baumeler and C. H. Eugster, Helv. Chim. Acta, 1991, 74, 469;
(b) A. Baumeler and C. H. Eugster, Helv. Chim. Acta, 1992, 75, 773;
(c) Y. Yamano and M. Ito, Chem. Pharm. Bull., 1994, 42, 410; (d) Y.
Yamano and M. Ito, J. Chem. Soc., Perkin Trans. 1, 1995, 1895; see
also:; (e) Y. Yamano and M. Ito, J. Chem. Soc., Perkin Trans. 1, 1993,
1599; (f) ref. 4.
19 J. K. Stille, Angew. Chem., Int. Ed. Engl., 1980, 25, 508 and references
cited therein.
20 Data for 4: IR (KBr, cm−1) 3430, 3054, 3000, 2922, 1647, 1607, 1435,
1395, 1366, 1319, 1290, 1233, 1171, 1096, 1073, 1030; 1H NMR
(400 MHz, CDCl3) d 7.10 (d, 1H, J = 9.5 Hz), 6.62 (d, 1H, J =
15.1 Hz), 6.55 (dd, 1H, J = 15.1, 9.5 Hz), 5.87 (t, 1H, J = 6.6 Hz),
1 3 7 4
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 1 3 7 2 – 1 3 7 4