b-Vinyl-a,b-butenolide

(R = H)

[54145-07-2]  · C6H6O2  · b-Vinyl-a,b-butenolide  · (MW 110.12) (R = Me)

[78657-20-2]  · C7H8O2  · &AAlpha;-Methyl-b-vinyl-a,b-butenolide  · (MW 124.15) (R = SPh)

[81470-07-7]  · C12H10O2S  · &AAlpha;-Phenylthio-b-vinyl-a,b-butenolide  · (MW 218.29)

(lactone annulating reagent with 1,3-dicarbonyl compounds;1,2 an acceptor in 1,6-conjugate addition reactions with various nucleophiles3)

Alternate Name: 4-vinyl-2(5H)-furanone.

Physical Data: R = H, Me: oil. R = SPh: solid, mp 70 °C.

Solubility: sol CH2Cl2 and THF; slightly sol n-hexane.

Preparative Method: most conveniently prepared by sulfenylation of b-vinylbutyrolactone,1,2,4 easily accessible from 2-butene-1,4-diol and ethyl orthoacetate,5 followed by sulfoxide elimination (eq 1).

Handling, Storage, and Precautions: is relatively unstable, slowly changing into a polymeric white solid, even on refrigeration; however, a-phenylthio-b-vinylbutenolide is much more stable to storage.

Lactone Annulation.

Under basic conditions, 2-methylcyclohexane-1,3-dione adds to b-vinylbutenolide to give a 1,6-conjugate addition product, which then undergoes cyclization under the reaction conditions to yield hydroxybutenolides as a mixture of diastereomers at the C-6 position (eq 2).1

When the sodium enolates of b-keto esters react with b-vinylbutenolide in THF or DME, annulated butenolides are produced in moderate yields (eq 3).2 Racemic frullanolide, a typical allergenic eudesmanolide, has been synthesized from one of these annulated products.2

1,6-Conjugate Addition.

b-Vinylbutenolide reacts with various nucleophiles in 1,6-conjugate addition reactions. For example, treatment of this butenolide with Benzeneselenol provides the 1,6-conjugate adduct, accompanied by a small amount of the isomeric 1,4-adduct (eq 4).3

a-Phenylthio-b-vinylbutenolide.

This reagent is readily accessible from b-vinyl butyrolactone by an eliminative Pummerer rearrangement (eq 1). Annulation of activated carbonyl compounds affords oxygenated perhydrooxobenzofurans (eq 5).6 The phenylthiobutenolide has been used in the total synthesis of paniculide A, a highly oxygenated bisabolene,7 and avenaciolide, an antifungal mold metabolite.8

a-Methyl-b-vinylbutenolide.

This reagent is also useful for lactone annulating reactions with 1,3-dicarbonyl compounds under basic conditions.9,10

Related Reagents.

a,b-Butenolide; g-Butyrolactone; 1,3-Cyclohexanedione; Dihydro-5-(hydroxymethyl)-2(3H)-furanone; b-Propiolactone; b-Ethynyl-b-propiolactone; 2-Trimethylsilyloxyfuran.


1. Kido, F.; Fujishita, T.; Tsutsumi, K.; Yoshikoshi, A. CC 1975, 337.
2. Kido, F.; Tsutsumi, K.; Maruta, R.; Yoshikoshi, A. JACS 1979, 101, 6420.
3. Miyashita, M.; Yoshikoshi, A. S 1980, 664.
4. Iwai, K.; Kosugi, H.; Uda, H.; Kawai, M. BCJ 1977, 50, 242.
5. Kondo, K.; Mori, F. CL 1974, 741.
6. Kido, F.; Noda, Y.; Yoshikoshi, A. JACS 1982, 104, 5509.
7. Kido, F.; Noda, Y.; Yoshikoshi, A. CC 1982, 1209; T 1987, 43, 5467.
8. Kido, F.; Tooyama, Y.; Noda, Y.; Yoshikoshi, A. CL 1983, 881.
9. Kido, F.; Noda, Y.; Maruyama, T.; Kabuto, C.; Yoshikoshi, A. JOC 1981, 46, 4264.
10. Pennanen, S. I. SC 1985, 15, 865.

Fusao Kido

Tohoku University, Sendai, Japan



Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.