1
22
X. Ariza et al.
LETTER
emplify the usefulness of C -symmetric trans- and cis-2-
Mulzer, J.; Schaumann, E., Eds.; Thieme: Stuttgart, 1995; p
2
3301; (b) Pereira, S.; Srebnik, M. Aldrichim. Acta 1993, 26,
alkene-1,4-diols as precursors of b,g-trans and b,g-cis
paraconic acids. Extension of this methodology to a-me-
thylated paraconic acids by Claisen-type rearrangements
of propionyl derivatives is under investigation.
17.
(
12) Fiaud, J. C.; Malleron, J. L. J. Chem. Soc., Chem. Commun.
1981, 1159.
(
(
(
13) Negishi, E.; John, R. A. J. Org. Chem. 1983, 48, 4098.
14) Trost, B. M.; Keinan, E. Tetrahedron Lett. 1980, 21, 2591.
15) Preparation of (4S,5S)-4-[(E)-Hept-1-enyl)]-5-pentyl-4,5-
dihydro-(3H)-furan-2-one (trans-7): To a solution of (S,S)-
Acknowledgement
1
1 (120 mg, 0.38 mmol) and t-BuMe SiCl (239 mg,
This work has been supported by the Ministerio de Educación y
Cultura (PB98-1272, DGESIC) and Direcció General de Recerca,
Generalitat de Catalunya (1996SGR00102). We also thank Univer-
sitat de Barcelona for a doctorate studentship to M.L., and Prof. J.
Vilarrasa for reading the draft.
2
1.53 mmol) in anhyd THF (4 mL) at -78 °C under argon, a
toluene solution of KHMDS (0.5 M, 2.30 mL, 1.15 mmol) was
added dropwise, and the mixture was stirred at r.t. overnight.
Then, most of the solvent was removed under vacuum, anhyd
toluene (8 mL) was added and the mixture was heated (130 °C
bath temperature) for 10 h. The reaction mixture was
References and Notes
partitioned by adding diethyl ether (50 mL) and brine (10 mL).
The aqueous layer was washed with additional diethyl ether
(
1) (a) Petragnani, N.; Ferraz, H. M. C.; Silva, G. V. J. Synthesis
986, 157; (b) Hoffmann, H. M. R.; Rabe, J. Angew. Chem.
(
10 mL) and the organic layers were dried (MgSO ), and
4
1
concentrated in vacuo. The residue was filtered through a pad
of silica gel and the mixture of the acid threo-13a and its silyl
ester (threo-13b) was treated with THF (2 mL) and aq LiOH
Int. Ed. 1985, 24, 94.
(2) Park, B. K.; Nakagawa, M.; Hirota, A.; Nakayama, M. J.
Antibiot. 1988, 41, 751.
(
8 M, 1 mL) at 70 °C for 9 h. The solution was then acidified
(
3) Mahato, S. B.; Siddiqui, K. A. I.; Bhattacharya, G.; Ghosal,
T.; Miyahara, K.; Sholichin, M.; Kawasaki, T. J. Nat. Prod.
with aq HCl (2 M, 6 mL), additional THF (3 mL) was added
and the mixture was heated al 50 °C for 6 h. The mixture was
partitioned by adding CH Cl (50 mL), and the organic layer
1987, 50, 245.
2
2
(
4) For leading references, see: (a) Bella, M.; Margarita, R.;
Orlando, C.; Orsini, M.; Parlanti, L.; Piancatelli, G.
was dried (MgSO ). Evaporation of solvents and purification
4
by flash chromatography on silica gel gave (95: 5 hexane/
EtOAc) trans-7 as a yellowish oil (68 mg, 70% overall yield).
Data for (4S,5S)-4-[(E)-hept-1-enyl)]-5-pentyl-4,5-dihydro-
Tetrahedron Lett. 2000, 41, 561; (b) Masaki, Y.; Arasaki, H.;
Itoh, A. Tetrahedron Lett. 1999, 40, 4829; (c) Lu, X.; Zhu, G.;
Wang, Z. Synlett 1998, 115, and references therein; (d) Sibi,
M. P.; Deshpande, P. K.; La Loggia, A. J. Synlett 1996, 343;
(
[
0
1
3H)-furan-2-one (trans-7): R 0.73 (65:35 hexane/EtOAc);
f
1
20
a]D -52.9 (c = 1.8, CHCl ); H NMR (CDCl , 300 MHz) d
3
3
(e) Saicic, R. N.; Zard, S. Z. Chem. Commun. 1996, 1631;
.90 (t, 6H, J = 7.0 Hz, CH CH ), 1.27-1.65 (m, 14H, CH ),
3
2
2
(f) Drioli, S.; Felluga, F.; Forzato, C.; Nitti, P.; Pitacco, G.
.95-2.05 (m, 2H, CH CH=CH), 2.41 (dd, 1H, J = 16.5, 10.0
2
Chem. Commun. 1996, 1289; (g) Vaupel, A.; Knochel, P. J.
Org. Chem. 1996, 61, 5743; (h) Takahata, H.; Uchida, Y.;
Momose, T. J. Org. Chem. 1995, 60, 5628; (i) Banks, M. R.;
Dawson, I. M.; Gosney, I.; Hodgson, P. K. G.; Thorburn, P.
Tetrahedron Lett. 1995, 36, 3567; (j) Mulzer, J.; Salimi, N.;
Hartl, H. Tetrahedron:Asymmetry 1993, 4, 457; (k) de
Azevedo, M. B. M.; Murta, M. M.; Greene, A. E. J. Org.
Chem. 1992, 57, 4567.
Hz, HCH’CO ), 2.60-2.80 (m, 2H, HCH’CO and
2
2
CHCH=CH), 4.10 (td, 1H, J = 8.2, 3.4 Hz, CHO), 5.25 (dd,
H, J = 15.3, 8.7 Hz, CH CH=CH), 5.55 (dt, 1H, J = 15.3, 6.9
1
2
13
Hz, CH CH=CH); C NMR (CDCl , 75.4 MHz) d 13.8
(
2
3
CH (CH ) ), 13.9 (CH (CH ) ), 22.4, 25.4, 28.7, 30.8, 31,2,
3 2 4 3 2 4
3
1.4, 32.3, 33.4 and 36.0 (CH ), 45.5 (CHCH CH), 85.3
2
(
(
CHO), 127.3 (CH = CHCH ), 134.3 (CH=CHCH ), 176.0
C=O); IR (film) 2930, 1785, 1466, 1204; HRMS (M ) calcd
2
2
+
(
5) For recent approaches, see: (a) Forster, A.; Fitremann, J.;
Renaud, P. Tetrahedron Lett. 1998, 39, 7097 and references
therein; (b) Drioli, S.; Felluga, F.; Forzato, C.; Nitti, P.;
Pitacco, G.; Valentin, E. J. Org. Chem. 1998, 63, 2385;
for C H O :252.2089, found 252.2080.
1
6
28
2
Data for (4R,5S)-4-[(E)-Hept-1-enyl)]-5-pentyl-4,5-
dihydro-(3H)-furan-2-one (cis-7) : Yellowish oil; R 0.35
f
20
1
(
(
1
(
9:1 hexane/EtOAc); [a]D -37.7 (c = 0.53, CHCl ); H NMR
3
(
c) Drioli, S.; Felluga, F.; Forzato, C.; Nitti, P.; Pitacco, G.;
Valentin, E. J. Mol. Catal. Part B: Enzymatic 1997, 3, 203;
d) Jacobi, P. A.; Herradura, P. Tetrahedron Lett. 1996, 37,
297.
CDCl , 300 MHz) d 0.88 (t, 6H, J = 6.9 Hz, CH CH ), 1.27-
3
3
2
.57 (m, 14H, CH ), 1.98-2.08 (m, 2H, CH CH=CH), 2.38
2
2
(
8
dd, 1H, J = 17.4, 5.5 Hz, HCH’CO ), 2.68 (dd,1H, J = 17.4,
2
7
.9 Hz, HCH’CO ), 3.04-3.14 (m, 1H, CHCH=CH), 4.42-
2
(
6) (a) Bach, J.; Berenguer, R.; Garcia, J.; López, M.; Manzanal,
J.; Vilarrasa, J. Tetrahedron 1998, 54, 14947; (b) Bach, J.;
Berenguer, R.; Garcia, J.; Loscertales, T.; Manzanal, J.;
Vilarrasa, J. Tetrahedron Lett. 1997, 38, 1091.
4.50 (m, 1H, CHO), 5.33 (dd, 1H, J = 15.6, 8.7 Hz,
CH CH=CH), 5.54 (td, 1H, J = 15.6, 6.6 Hz, CH CH=CH);
2
2
13
C NMR (CDCl , 75.4 MHz) d 14.0 (CH (CH ) ), 14.1
CH (CH ) ), 22.5, 25.3, 28.8, 30.8, 31,3, 31.6, 32.4, 33.4 and
3
3
2 4
(
3 2 4
(
(
7) Chabaud, B.; Sharpless, K. B. J. Org. Chem. 1979, 44, 4202.
8) An attempt to obtain (S,S)-5 by double addition of acetylene
to hexanal, promoted by Zn(OTf) and Et N in the presence of
3
5.4 (CH ), 42.3 (CHCH=CH), 83.7 (CHO), 125.4
2
(
2
CH=CHCH ), 134.4 (CH=CHCH ), 176.6 (C=O); IR (film)
2
2
2
3
+
940, 1780, 1458, 1210; HRMS (M ) calcd for
(
-)-N-methylephedrine, failed. See: Frantz, D. E.; Fässler, R.;
C H O :252.2089, found 252.2096.
1
6
28
2
Carreira, E. M. J. Am. Chem. Soc. 2000, 122, 1806.
9) For a review, see: Corey, E. J.; Helal, C. J. Angew. Chem. Int.
Ed. 1998, 37, 1986.
(
16) Spectral data of cis- and trans-6 fully agree with those
reported in ref. 5c and 4g.
17) Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B.
J. Org. Chem. 1981, 46, 3936.
(
(
(
10) The observed stereoselectivity depends on the amount of
catalyst used. For instance: i) 2 equiv. of 9, >99% e.e., dl/
meso = 12:1; ii) 1.0 equiv. of 9, >99% e.e., dl/meso = 5.7:1;
iii) 0.2 equiv. of 9, 99% e.e., dl/meso = 2.8:1.
Article Identifier:
437-2096,E;2001,0,01,0120,0122,ftx,en;L17900ST.pdf
(
11) (a) For a detailed review on [3,3] sigmatropic rearrangements,
see: Frauenrath, H. In Houben-Weyl Methods of Organic
Chemistry, Vol. E21; Helmchen, G.; Hoffmann, R. W.;
1
Synlett 2001, No. 1, 120–122 ISSN 0936-5214 © Thieme Stuttgart · New York