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A.-F. Salit et al.
LETTER
(4) (a) Silva, M.; Bittner, M.; Sammes, P. G. Phytochemistry
1973, 12, 883. (b) Ying, B.-P.; Kubo, I.; Chairul;
Matsumoto, T.; Hayashi, Y. Phytochemistry 1990, 29,
3953. (c) Kubo, I.; Himejima, M.; Ying, B.-P.
Phytochemistry 1991, 30, 1467. (d) Pettit, G. R.; Tan, R.;
Herald, D. L.; Hamblin, J.; Pettit, R. K. J. Nat. Prod. 2003,
66, 276.
(5) Lee, H.-J.; Lee, C.-H.; Chung, M.-C.; Chun, H.-K.; Rhee,
J.-S.; Kho, Y.-H. Tetrahedron Lett. 1999, 40, 6949.
(6) Chiaroni, A.; Riche, C.; Khuong-Huu, Q.; Nguyen-Ngoc,
H.; Nguyen-Viet, K.; Khuong-Huu, F. Acta Crystallogr.,
Sect. C 2000, 56, 711.
J = 9.9, 1.1 Hz, 1 H), 5.90 (dd, J = 9.9, 1.8 Hz, 1 H), 5.76 (m,
1 H), 4.83 (m, app. br d, J = 1.2 Hz, 2 H), 3.74 (t, J = 6.3 Hz,
2 H), 2.46–2.41 (m, 2 H), 1.04 (s, 9 H). 13C NMR (100 MHz,
CDCl3): d = 164.1 (s), 139.0 (d), 135.5 (d, 4 C), 133.4 (s,
3 C), 131.7 (d), 129.8 (d, 2 C), 127.7 (d, 4 C), 119.0 (d), 71.1
(t), 62.5 (t), 31.0 (t), 26.8 (q, 3 C), 19.1 (s). MS (EI, 70 eV):
m/z (%) = 377 (1) [M – Me+], 355 (64) [M – t-Bu+], 307 (9),
306 (27), 305 (100), 257 (19), 227 (17), 200 (15), 199 (80),
197 (16), 183 (13), 181 (18), 167 (7), 135 (18), 105(10), 91
(6), 77 (12). HRMS–FAB: m/z calcd for C24H28NaO3Si [M +
Na+]: 415.1699; found: 415.1692.
(20) Alonso, D. A.; Najera, C.; Sansano, J. M. Tetrahedron 1994,
50, 6603; compound 12 is sensitive and can undergo
polymerization upon concentration of its solutions.
(21) (Z)-5-[(tert-Butyldiphenylsilyloxy)propylidene]-5,6-
dihydropyran-2-one (10c)
(7) Teruya, T.; Suenaga, K.; Maruyama, S.; Kurotaki, M.;
Kigoshi, H. Tetrahedron 2005, 61, 6561.
(8) Choi, T.-L.; Grubbs, R. H. Chem. Commun. 2001, 2648.
(9) Vedrenne, E.; Royer, F.; Oble, J.; El Kaïm, L.; Grimaud, L.
Synlett 2005, 2379.
IR: 1719, 1644, 1427, 1221, 1104, 937, 820, 738, 700, 613
cm–1. 1H NMR (400 MHz, CDCl3): d = 7.65–7.62 (m, 4 H),
7.46–7.37 (m, 6 H), 6.92 (d, J = 9.7 Hz, 1 H), 5.85–5.81 (m,
2 H), 5.00 (m, app. br s, 2 H), 3.75 (t, J = 6.2 Hz, 2 H), 2.33
(dt, app. q, J = 6.4 Hz, 2 H), 1.04 (s, 9 H). 13C NMR (100
MHz, CDCl3): d = 163.7 (s), 145.0 (d), 135.5 (d, 4 C), 133.8
(d), 133.3 (s, 2 C), 129.8 (d, 2 C), 128.7 (s), 127.7 (d, 4 C),
116.7 (d), 66.6 (t), 62.3 (t), 31.6 (t), 26.8 (q, 3 C), 19.1 (s).
HRMS–FAB: m/z calcd for C24H28NaO3Si [M + Na+]:
415.1699; found: 415.1693.
(10) Trnka, T. M.; Day, M. W.; Grubbs, R. H. Organometallics
2001, 20, 3845.
(11) For a review, see: Diver, S. T.; Giessert, A. J. Chem. Rev.
2004, 104, 1317.
(12) Propargyl acrylate did not react with olefin 11 by ene-yne
cross-metathesis [Grubbs II (5–10 mol%), CH2Cl2, reflux,
4–8 h; trace of lactones 10a,c detected by TLC] and did also
not produce the g-methylene a,b-unaturated lactone 12 by
ene-yne RCM (vide infra).
(13) For a review on macrocyclizations by RCM (including
1,3-dienes as olefinic partners), see: Gradillas, A.; Pérez-
Castells, J. Angew. Chem. Int. Ed. 2006, 45, 6086.
(14) For cross-metathesis involving conjugated dienes, see:
(a) Funk, T. W.; Efskind, J.; Grubbs, R. H. Org. Lett. 2005,
7, 187. (b) Ferrié, L.; Amans, D.; Reymond, S.; Bellosta, V.;
Capdevielle, P.; Cossy, J. J. Organomet. Chem. 2006, 691,
5456. (c) Moura-Letts, G.; Curran, D. P. Org. Lett. 2007, 9,
5.
(15) Some lactones of type B have been prepared by a Pd-
catalyzed annulation of allenes with (Z)-3-iodoacrylic acid,
see: Larock, R. C.; He, Y.; Leong, W. W.; Han, X.; Refvik,
M. D.; Zenner, J. M. J. Org. Chem. 1998, 63, 2154;
unfortunately, the reaction proceeds with low
(22) For a similar observation in the cross-metathesis between
1,2-substituted-1,3-butadienes and 1-alkenes, see ref. 14a.
(23) Tan, Z.; Negishi, E. Angew. Chem. Int. Ed. 2006, 45, 762.
(24) Liron, F.; Fosse, C.; Pernolet, A.; Roulland, E. J. Org. Chem.
2007, 72, 2220.
(25) Roulland, E. Angew. Chem. Int. Ed. 2008, 47, 3762.
(26) For other syntheses of haterumalide NA, see: (a) Kigoshi,
H.; Kita, M.; Ogawa, S.; Itoh, M.; Uemura, D. Org. Lett.
2003, 5, 957. (b) Gu, Y.; Snider, B. B. Org. Lett. 2003, 5,
4385. (c) Hoye, T. R.; Wang, J. J. Am. Chem. Soc. 2005,
127, 6950. (d) Hayakawa, I.; Ueda, M.; Yamuara, M.; Ikeda,
Y.; Suzuki, Y.; Yoshizato, K.; Kigoshi, H. Org. Lett. 2008,
10, 1859.
(27) Tennyson, R. L.; Cortez, G. S.; Galicia, H. J.; Kreiman,
C. R.; Thompson, C. M.; Romo, D. Org. Lett. 2002, 4, 533.
(28) The geometric isomers (Z/E = 95:5) were easily separated
by flash chromatography.
(29) Li, J.; Xu, X.; Zhang, Y. Tetrahedron Lett. 2003, 44, 9349.
(30) (E)-3-(4,4-Dichlorobut-3-enylidene)-6-methoxy-3,6-
dihydro-2H-pyran (22)
regioselectivity for monosubstituted allenes.
(16) The a-bromoenals were prepared from the corresponding
enals, see: Kowalski, C. J.; Weber, A. E.; Fields, K. W.
J. Org. Chem. 1982, 47, 5088.
(17) Molander, G. A.; Felix, L. A. J. Org. Chem. 2005, 70, 3950.
(18) These compounds were prepared by Pd-catalyzed
hydrostannylation of the corresponding acetylenic esters
followed by iododestannylation, see: (a) Zhang, H. X.;
Guibé, F.; Balavoine, G. J. Org. Chem. 1990, 55, 1857.
(b) Rossi, R.; Carpita, A.; Cossi, P. Tetrahedron 1992, 48,
8801.
IR: 1684, 1619, 1446, 1384, 1300, 1187, 1158, 1103, 956,
872, 749 cm–1. 1H NMR (400 MHz, CDCl3): d = 6.61 (d,
J = 10.2 Hz, 1 H), 5.95–5.83 (m, 1 H), 5.82 (t, J = 7.4 Hz,
1 H), 5.29 (t, J = 7.8 Hz, 1 H), 4.91 (d, J = 2.8 Hz, 1 H), 4.49
(d, AB syst, J = 13.0 Hz, 1 H), 3.99 (d, AB syst, J = 13.0 Hz,
1 H), 3.45 (s, 3 H), 3.02 (app. td, J = 7.6, 1.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 130.9 (s), 127.0 (d),
126.6 (d), 123.7 (d), 121.7 (d), 121.3 (s), 95.5 (d), 62.6 (t),
55.4 (q), 27.2 (t). HRMS–FAB: m/z calcd for
(19) (E)-5-[(tert-Butyldiphenylsilyloxy)propylidene]-5,6-
dihydropyran-2-one (10a)
IR: 1721, 1427, 1391, 1248, 1221, 1199, 1091, 1027, 820,
786, 733, 700, 613 cm–1. 1H NMR (400 MHz, CDCl3):
d = 7.64–7.62 (m, 4 H), 7.46–7.36 (m, 6 H), 7.21 (dd,
C10H1235Cl2NaO2 [M + Na+]: 257.01066; found: 257.01065.
Synlett 2008, No. 17, 2583–2586 © Thieme Stuttgart · New York