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32. Experimental section: General remarks. 1H and 13C NMR spectra were recorded
on a 300 MHz or a 400 MHz spectrometer as noted. GC/MS (using a HP-1 fused
silica capillary column) and direct insertion spectra (EI) were measured at
70 eV. Elemental analyses were performed at the Instrumental Analysis Center
of the Chemistry Department, Chemistry Institute of the University of São Paulo.
Reaction flasks and syringes were oven-dried (120 °C) before use. Melting
points (uncorrected) were determined on a Kofler hot plate. All reactions were
carried out under an atmosphere of dry nitrogen and monitored by TLC using
prepared plates (Silica Gel 60 F254 on aluminum). The chromatograms were
observed by the use of UV or the developing agent ethanolic vanillin. Merck
silica gel (230–400 mesh) was used for flash chromatography. THF was distilled
over sodium/benzophenone immediately before use. Dibutyl ditelluride was
prepared by the method reported in the literature.43
33. Typical procedure for (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2.22 To a
solution of 1-methoxy-but-1-en-3-yne 1 (sol 50% water/methanol 1:4; 0.640 g,
1.0 ml, 8.0 mmol) and dibutyl ditelluride (0.738 g, 2.0 mmol) in ethanol (80 ml)
at room temperature under nitrogen, sodium borohydride (0.22 g, 6.0 mmol)
was added. After the end of the addition, the yellow mixture was heated at
reflux for 28 h. Then it was cooled to room temperatue, diluted with ethyl
acetate (60 ml), and washed with NH4Cl saturated solution (3 ꢂ 25 ml). After
the organic phase was dried over anhydrous MgSO4, the solvent was removed
under reduced pressure and the residue purified by flash chromatography on
silica gel with hexane/ethyl acetate (9:1) as the mobile phase. After
evaporation of hexane, compound 2, which is very stable, was obtained as a
yellow–orange oil. Yield: 0.7574 g (70%). MS m/z 270 (56.05) C9H16OTe, 213
(40.18) (–C4H9), 84 (100.00) (–C4H9Te); 1H NMR (300 MHz) (d in CDCl3) 0.91
(3H, t, J = 7 Hz, 4-H3), 1.48 (2H, sext, J = 7 Hz, 3-H2), 1.78 (2H, quint, J = 7 Hz, 2-
H2), 2.64 (2H, t, J = 7 Hz, 1-H2), 3.64 (3H, s), 4.96 (1H, ddd, J3,4 = 10.4 Hz,
J2,3 = 6.6 Hz, J1,3 ꢁ0.7 Hz, 3-H), 5.92 (1H, dq, J3,4 = 6.6 Hz, J ꢁ1.0 Hz, J ꢁ0.7 Hz, 4-
H), 6.45 (1H, ddd, J1,2 = 10.5 Hz, J1,3 ꢁ1.0, J1,4 ꢁ0.7 Hz, 1-H), 6.91 (1H, dd,
J1,2 = 10.5 Hz, J2,3 = 10.4 Hz, 2-H). 13C NMR 6.4, 13.4, 24.9, 34.1, 60.1, 101.1,
108.1, 131.6, 148.8. Anal. Calcd for C9H16OTe: C, 40.36; H, 6.02. Found: C,
40.73; H, 5.99.
34. Te/Li exchange reaction on (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2.22
To a solution of 2 (0.267 g, 1.0 mmol) in THF (8.0 ml), cooled to ꢀ78 °C under
N2, BuLi (0.76 ml, 1.1 mmol, 1.43 M) was added in one portion. The reaction
mixture was stirred at this temperature and after 1.0 min, the butadienyl
lithium 3 formed can be used in situ. The observations of the reactions of this
intermediate (total disappearance of 9 followed by TLC and formation of only
one product) indicated that it is formed in high yield.
35. Typical procedure for (1Z,3Z)-1-methoxy-5-hydroxy-butyl-1,3-pentadiene 4b. To a
solution of butadienyl lithium 10 formed as above, freshly distilled
pentanaldehyde (0.101 ml; 1.0 mmol) was added at ꢀ78 °C and stirred for
30 min at this temperature, then allowed to reach room temperature and
stirred for an additional 30 min. The solution was treated with a saturated
solution of NH4Cl, diluted with ether (30 ml) and washed with saturated NH4Cl
solution (3 ꢂ 15 ml). After the organic phase was dried over anhydrous MgSO4,
the solvent was removed under reduced pressure, resulting in a pale-yellow
liquid. Yield: 0.10 g (75% yield). Compound 4b can be further purified by flash
15. (a) Shimizu, M.; Nakamaki, C.; Shimono, K.; Schelper, M.; Kurahashi, T.;
Hiyama, T. J. Am. Chem. Soc. 2005, 127, 12506–12507; (b) Molander, G. A.;
Yokoyama, Y. J. Org. Chem. 2006, 64, 8873.
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3671–3675; (b) Denmark, S. E.; Tymonko, S. A. J. Am. Chem. Soc. 2005, 127,
8004–8005.
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Org. Chem. 2000, 65, 1780–1787; (b) Ikegashira, K.; Nishihara, Y.; Hirabayashi,
K.; Mori, A.; Hiyama, T. Chem. Commun. 1997, 1039–1040.
chromatography using
a mixture of ethyl acetate/hexane (8:2) as eluent.
18. (a) Semmelhack, M. F.; Helquist, P.; Jones, L. D.; Keller, L.; Mendelson, L.; Ryono,
L. S.; Smith, J. G.; Stauffer, R. D. J. Am. Chem. Soc. 1981, 103, 6460–6471; (b)
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2000, 65, 4575–4583.
However, prolonged contact with SiO2 must be avoided since it causes
hydrolysis of 4b to form compound 5b. MS m/z 170 (16.14), 128 (6.89), 113
(100.00) [MꢀC4H9]+, 85 (36.26), 55 (19.23), 45 (30.67);
m
max 3383, 2931–2857,
1649, 1606, 1456, 1420, 1263, 1108, 1018, 929, and 753 cmꢀ1
;
1H NMR
19. (a) Takahashi, T.; Xi, Z.; Obora, Y.; Suzuki, N. J. Am. Chem. Soc. 1995, 117, 2665–
2666; (b) Okukado, N.; Van Horn, D. E.; Klima, W. L.; Negishi, E. Tetrahedron
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N.; Nakajima, K.; Takahashi, T. J. Am. Chem. Soc. 1997, 119, 12842–12848;
(300 MHz) (d in CDCl3) 0.85 (3H, t, J = 7.5 Hz, 9-H3), 1.30 (2H, sext, J = 7 Hz, 8-
H2), 1.45 (2H, quint, J = 7 Hz, 7-H2), 1.54 (2H, quart, J = 7 Hz, 6-H2), 2.30 (1H, br
s, OH), 3.60 (3H, s, OCH3), 4.05 (1H, dt, J5,6 = 7, J5,4 = 7 Hz, 7-H2), 4.45 (1H, dd,
J4,5 = 1.4, J3,4 = 10 Hz, 4-H), 5.25 (1H, m), 5.95 (1H, d, J1,2 = 6.9 Hz, 1-H), 6.35