S. Bouquillon, J. Muzart
FULL PAPER
[
[
[
[
2] [2a]
B. M. Trost, Tetrahedron 1977, 33, 2615Ϫ2649. Ϫ [2b] B. M.
Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395Ϫ422.
J.-C. Fiaud, J.-L. Malleron, Tetrahedron Lett. 1981, 22,
399Ϫ1402.
B. M. Trost, N. R. Schmuff, Tetrahedron Lett. 1981, 22,
999Ϫ3000.
B. M. Trost, R.C. Bunt, J. Am. Chem. Soc. 1996, 118, 235Ϫ236.
2-butene (19 mL, 0.23 mol) in dichloromethane (20 mL) at 0° under
argon, followed by dropwise addition of pyridine (56 mL, 0.70
mol). After 30 min., the mixture was allowed to warm to room
temperature and stirring continued for 18 h. The mixture was ex-
tracted with dichloromethane and the organic phase successively
washed with 2 HCl and saturated NaCl solution. After drying
over magnesium sulfate and evaporation of the solvent, distillation
3]
4]
5]
1
2
[6] [6a]
G. C. Lloyd-Jones, S. C. Stephen, Chem. Commun. 1998,
1
led to 1 (34.5 g, 88% yield). b.p. 50 °C/0.05 mbar. Ϫ H NMR: δ ϭ
[6b]
2
321Ϫ2322. Ϫ
Eur. J. 1998, 4, 2539Ϫ2549. Ϫ
Y. Uozumi, J. Am. Chem. Soc. 1998, 120, 1681. Ϫ
G. C. Lloyd-Jones, S. C. Stephen, Chem.
2
2
.05 (s, 6 H, CH
H, CHϭCH). Ϫ C NMR: δ ϭ 20.5 (CH
3
COO), 4.62 (d, J ϭ 5.5 Hz, 2 H, OCH
2
), 5.64 (m,
[6c]
T. Hayashi, M. Kawatsura,
13
[6d]
3
), 59.7 (OCH ), 127.8
2
S. Vys-
(CHϭCH), 170.2 (CϭO).
kovic, M. Smrciona, V. Hanus, M. Polasek, P. Kocovsky, J. Org.
Chem. 1998, 63, 7738Ϫ7748. Ϫ [ G. C. Lloyd-Jones, S. C.
Stephen, M. Murray, C. P. Butts, S. Vyskocil, P. Kocovsky,
Chem. Eur. J. 2000, 6, 4348Ϫ4357. Ϫ [ G. C. Lloyd-Jones,
Synlett 2001, 161Ϫ183.
6e]
(
E)-1,4-Diacetoxy-2-butene (2)[33Ϫ35]
6f]
Method A:
A
solution of (E)-1,4-dibromo-2-butene (5 g,
23.3 mmol) and potassium acetate (5 g, 51.0 mmol) in glacial acetic
[7]
C. Amatore, A. Jutand, G. Meyer, L. Mottier, Chem. Eur. J.
acid (20 mL) was refluxed for 24 h. After filtration of the resulting
potassium bromide and evaporation of acetic acid, distillation pro-
vided 2 (3.2 g, 80% yield). b.p. 120 °C/21 mbar.
1999, 5, 466Ϫ473.
[
8]
[8a]
See also:
B. Äkermark, G. Äkermark, L. S. Hegedus, K.
[
8b]
Zetterberg, J. Am. Chem. Soc. 1981, 103, 3037Ϫ3040. Ϫ
B. Äkermark, S. Hansson, B. Krakenberger, A. Vitagliano, K.
Method B: Adapted from a Z/E-isomerization procedure in the lit-
Zetterberg, Organometallics 1984, 3, 679Ϫ682.
[
18,36]
[9]
3
erature.
A solution of 1 (765 mg, 4.45 mmol) and PhSSPh
A neutral η -allylpalladium intermediate could be involved
(
975 mg, 4.47 mmol) in cyclohexane (60 mL) was deoxygenated by
when using 2-diphenylphosphanyl-2Ј-methoxy-1,1Ј-binaphthyl
as a ligand: [ T. Hayashi, M. Kawatsura, Y. Uozumi, Chem.
9a]
bubbling with argon for 10 min. and then irradiated at λ Ͼ 290 nm
for 3 h. After evaporation of the solvent, purification of the residue
by flash chromatography led to 2 (617 mg, 81% yield). Ϫ H NMR:
δ ϭ 2.06 (s, 6 H, CH
(
1
Commun. 1997, 561Ϫ562. Ϫ [
Chem. 1999, 576, 195Ϫ202.
9b]
T. Hayashi, J. Organomet.
1
[
10]
M. M. L. Crilley, B. T. Golding, C. Pierpoint, J. Chem. Soc.,
Perkin Trans. 1 1988, 2061Ϫ2067.
3
COO), 4.58 (d, J ϭ 5.5 Hz, 4 H, OCH
m, 2 H, CHϭCH). Ϫ 13C NMR: δ ϭ 20.8 (CH
), 63.9 (OCH
2
2
), 5.85
3
),
[
11] [11a]
K. Kaneda, H. Kurosaki, M. Terasawa, T. Imanaka, S.
28.1 (CHϭCH), 172.0 (CϭO).
[11b]
Teranishi, J. Org. Chem. 1981, 46, 2356Ϫ2362. Ϫ
B. T.
,2-Diacetoxy-3-butene (3):[34,35] Prepared from 1,2-diol-3-butene
Golding, C. Pierpoint, R. Aneja, J. Chem. Soc., Chem. Com-
1
(
mun. 1981, 1030Ϫ1031. Ϫ [
11c]
E. Curzon, B.T. Golding, C.
3 g, 34.1 mmol) as described in the literature.[ Ϫ H NMR: δ ϭ
34]
1
Pierpoint, B.W. Waters, J. Organomet. Chem. 1984, 262,
2
.07 (s, 3 H, CH
1.8, 7.2 Hz, 1 H, CH
OAc), 5.26 (dt, J ϭ 10.7, 1.1 Hz, 1 H, CHϭCH
J ϭ 17.2, 1.1 Hz, 1 H, CHϭCH ), 5.49 (m, 1 H, CHOAc), 5.74
ddd, J ϭ 17.2, 10.7, 6.1 Hz, 1 H, CHϭCH
). Ϫ 13C NMR: δ ϭ
0.7 and 20.9 (2 CH ), 64.7 (CH OAc), 72.0 (CHOAc 128.1 (CHϭ
CH ), 132.2 (CHϭCH ), 170.6 (CϭO).
3
COO), 2.10 (s, 3 H, CH
OAc), 4.22 (dd, J ϭ 11.8, 3.8 Hz, 1 H,
), 5.31 (dt,
3
COO), 4.07 (dd, J ϭ
[11d]
2
63Ϫ269. Ϫ
T. Mandai, S. Hashio, J. Goto, M. Kawada,
1
CH
2
[11e]
Tetrahedron Lett. 1981, 22, 2187Ϫ2190. Ϫ
T. Mandai, K.
2
2
Hara, M. Kawada, J. Nokami, Tetrahedron Lett. 1983, 24,
2
1577Ϫ1518.
[12] [12a]
(
2
2
B. M. Trost, T. R. Verhoeven, J. M. Fortunak, Tetrahedron
Lett. 1979, 2301Ϫ2304. Ϫ [
J. Am. Chem. Soc. 1980, 102, 4730Ϫ4743.
12b]
B. M. Trost, T. R. Verhoeven,
3
2
2
2
[
[
13]
[2b]
The epimerization is due
either to a return reaction of the
acetate anion[ or to a redox transmetallation of the η -allyl-
12]
3
General Isomerization Procedure and Determination of the Acetate
Ratios: Pd(PPh (0.168 g, 0.05 equiv.) was added to a solution of
, 2 or 3 (2.90 mmol) in dry THF or DMF (15 mL) under argon
palladium intermediate by the catalyst.[
14]
3 4
)
14] [14a]
T. Takahashi, Y. Jinbo, K. Kitamura, J. Tsuji, Tetrahedron
1
Lett. 1984, 25, 5921Ϫ5924. Ϫ [
B. Bosnisch, J. Am. Chem. Soc. 1985, 107, 2046Ϫ2054. Ϫ
M. Moreno-Manas, J. Ribas, A. Virgili, J. Org. Chem. 1988,
14b]
P. B. Mackenzie, J. Whelan,
and the mixture was warmed in a bath heated at 70Ϫ72 °C.
Samples were taken at the times reported in the tables and then
filtered through Celite. After evaporation of the solvent and addi-
tion of TMS/CDCl , the ratios between the different acetates were
3
established from the H NMR spectra and the respective integra-
tions of the CH protons of 1 (δ ϭ 4.62) and 2 (δ ϭ 4.58) and the
[
14c]
[14d]
5
3, 5328Ϫ5335. Ϫ
H. Kurosawa, S. Ogoshi, N. Chatani,
Y. Kawasaki, S. Murai, I. Ikeda, Chem. Lett. 1990, 1745Ϫ1748.
1
[14e]
Ϫ
J.-E. Bäckvall, K. L. Granberg, A. Heumann, Israel J.
[14f]
2
Chem. 1991, 31, 17Ϫ24. Ϫ
K. L. Granberg, J.-E. Bäckvall,
J. Am. Chem. Soc. 1992, 114, 6858Ϫ6863. Ϫ [
14g]
S. Ogoshi, H.
CH proton of 3 (δ ϭ 5.74); the precision of the integrations was
estimated to be Ϯ3%.
[
14h]
Kurosawa, Organometallics 1993, 12, 2869Ϫ2871. Ϫ
M.
Moreno-Manas, L. Morral, R. Pleixats, J. Org. Chem. 1998,
Supporting Information Available: Tables S1ϪS4 and Figure S1 (see
also footnote on the first page of this article).
63, 6160Ϫ6166.
[
[
15]
0
With a diphosphane as ligand, the oxidative addition of Pd to
[
14b,14f]
allylic acetates could be an irreversible step,
in particular
when an excess of nucleophile is added.[
6a,6b]
16] [16a]
J.-P. Gen eˆ t, M. Balabane, J. E. Bäckvall, J. E. Nyström,
Acknowledgments
Tetrahedron Lett. 1983, 24, 2745Ϫ2748. Ϫ [
16b]
T. Tsuda, M.
Part of this work has been carried out in the framework of the
COST D12/0028/99 program. We are grateful to Claire Thorey for
preliminary experiments, to Engelhard Company for generous gifts
of palladium salts and to G. Lloyd-Jones for help with the text of
the manuscript.
Okada, S. Nishi, T. Saegusa, J. Org. Chem. 1986, 51, 421Ϫ426.
Ϫ [
16c]
Y. Uozumi, A. Tanahashi, T. Hayashi, J. Org. Chem.
[16d]
1993, 58, 6826Ϫ6832. Ϫ
ada, J. Am. Chem. Soc. 1999, 121, 7268Ϫ7269. Ϫ
N. Nomura, K. Tsurugi, M. Ok-
[16e]
G. Poli,
G. Giambastiani, A. Mordini, J. Org. Chem. 1999, 64,
16f]
2
962Ϫ2965. Ϫ [
M. J. Williams, Org. Lett. 1999, 1, 1969Ϫ1971. Ϫ
T. Kiyoi, T. Saegusa, J. Org. Chem. 1990, 55, 3388Ϫ3390. Ϫ
A. J. Blacker, M. L. Clarke, M. S. Loft, J.
[16g]
T. Tsuda,
[
1]
J. Tsuji, Palladium Reagents and Catalysts, Wiley, Chichester,
995, p. 290Ϫ395.
[
16h]
1
A. Yamazaki, K. Achiwa, Tetrahedron: Asymmetry 1995,
3304
Eur. J. Org. Chem. 2001, 3301Ϫ3305